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QUANTITATIVE
INORGANIC ANALYSIS
THEORY AND PRACTICE
BY
ARTHUR 1. VQ~, D.Sc. (LOND.), D.Le., F.R.t.O:.
HEAD OF CHEMISTRY DEPARTMENT, WOOLWICH POLYTECHNIC:
SOMETIMll BElT SCIENTIFIC RESEARCH FELLOW OF THE
IMPERIAL "COLLEGE, LONDON
SECOND EDITION
ANGRAU
545
N51VOG
Acc No. 1060
THE kind reception accorded to the First Edition has encouraged the
author in the belief that his main aims have been largely achieved.
These include the provision of a text-book which will be of value:
(i) to the student throughout the whole of his career and (ii) to practising
analytical chemists and to all those workers who have occasion to
utilise methods of quantitative inorganic analysis. .
During the eleven years that have elapsed since the previous
edition was published, inorganic analytical chemistry has developed
in numerous directions, more particularly in the introduction of in-
strumental methods of analysis. It is now generally accepted that a
training in at least some of the instrumental methods is highly desirable;
it is hoped that sufficientyew matter has been incorporated to meet
this objective. It will be appreciated that some instruments are
beyond the financial resources of the average College laboratory, and
an attempt. has been made to overcome this difficulty in a few cases
by supplying full details for the construction of home-made instru-
ments. Nevertheless, it is of t~e greatest importance that the balance
between what might be termed the classical method and the modern
instrumental method of training the student in inorganic analysis be
maintained; this can be achieved only if due emphasis be placed upon
classical methods in the course of instruction.
The task of revision has occupied several years, and new experi-
mental work carried out in the author's laboratory has been included.
In order to incorporate the very extensive changes and additions, the
book has been entirely reset. It may be regarded as virtually a new
work in which the desirable features of the First Edition have been
retained: the broad aim has been to present, as far as is possible within
the compass of a volume of moderate size, an up-to-date picture of
quantitative inorganic analysis. The task of selecting, checking, and
suitably arranging the extensive literature has not been easy; the
author ventures to hope that he has at least succeeded in giving a
reasonable account of the subjects which are of importance to the
student during his period of training in analytical chemistry. The
Selected Bibliography at the end of each chapter will assist the reader
in locating the sources where further information may be found. The
insertion of references to the literature throughout the text would have
increased the length (and the price) of the book considerably; this
feature, although of great value to advanced students and to practising
analysts, has, after very careful consideration, not been included in the
present edition. On the whole, it was decided that the volume was
sufficiently large as a text-book, and that the inclusion of Selected
Bibliographies might be acceptable as a reasonable compromise.
The text has been carefully revised, and due consideration has been
given to comments, criticisms, and suggestions made by teachers and
others throughout the world. The major changes in the Second
Edition may now be enumerated:
* v
vi Preface to Second Edition
-It
Chapter I (THE THEORETICAL BASIS OF QUANTITATIVE INORGANIO
ANALYSIS).
(i) Some of the Sections (e.g., determination of pH, experimental
details concerning potentiometric titrations, polarographic methods,
etc.) have been deleted, and are now included in an expanded form as
individual Chapters.
(ii) A brief account of Flame Photometry and of Emission Spectro-
graphy is given.
(iii) Table XVIII (Forms in which Elements and Radicals are
commonly Precipitated and Weighed in Gravimetric Analysis) has been
revised, and may be regarded as a summary of modern gravimetric
analvsis.
(i~) Section I. 62, on Organic Precipitants has been completely
revised.
(v) A new Section, I. 71, on the theory of the Electrolytic Separation
of Metals with Controlled Cathode Potential has been added, as has also a
brief account of Internal Electrolysis (I. 72).
Chapter II (EXPERIMENTAL TECHNIQUE OF QUANTITATIVE INORGANIC
ANALYSIS).
(i) Section II. 9 (Other Types of Balances) has been expanded
considerably.
(ii) Section II. 10D, includes an account of the mixed-resin procedure
for preparing pure water.
(iii) The tables of tolerances for volumetric apparatus have been
revised to conform with the pamphlet Tests on Volumetric Glassware
issued by the Metrology Division of the National Physical Laboratory
in January 1946.
(iv) Section II. 33 (Crucibles fitted with permanent porous plates) has
been revised and enlarged.
(v) A new Section, II. 39 (Reductions with metals), which includes an
account of the preparation and uses of the cadmium and silver reductors
and of amalgamated zinc spirals, has been introduced.
Chapter III (VOLUMETRIC ANALYSIS).
(i) The use of pure anhydrous potassium ferro cyanide in the
standardisation of potassium permanganate solutions (Sections III. 46,
and III. 48, Procedure D).
(ii) The determination of manganese in steel by the persulphate-
arsenite method (Section III. 61B).
(iii) The Sections dealing with Oxidations with Ceric Sulphate have
been considerably modified. New procedures are given for the.
preparation of ceric sulphate solutions (Section III. 74), the determina-
tion of copper (III. 79), and the determination of molybdenum (III. 80).
(iv) Sections 111.97, Reductions with Vanadous Salts (based upon the
work of C. M. Ellis in the author's laboratory), and III. 98, Reductions
with Chromous Salts, have been completely rewritten.
(v) An account is given of the preparation and uses of sodium starch
glycollate indicator (III. 100), anhydrous sodium thiosulphate as a
primary standard (III. 101 and III. 1040), the use of irreversible
indicators in potassium iodate titrations (Sections 111.122, and III. 125),
and the determination of iron with standard potassium iodate solution
(III. 133).
Preface to Second Edition vii
(vi) Under Miscellaneous Volumetric Determinations are included:
(a) orthophosphate (III, 146) ;
(b) hardness of water with disodium dihydrogen ethylenediamine
tetra-acetate (III, 148) ;
(c) ferric iron by titration with standard mercurous perchlorate
solution (III, 152) ;
(d) zirconium (III, 153) ;
(e) silica (III, 154) ;
(f) calcium by the urea hydrolysis method (III, 155); and
(g) fluorine by titration with standard thorium nitrate solution
(III, 156).
Chapter IV (GRAVIMETRIC ANALYSIS).
The new determinations of individual elements and radicals are too
numerous to be listed individually, but the following may be mentioned
by way of illustration:
(a) sulphate as barium sulphate using agar-agar as coagulant
(IV, 6);
(b) bismuth as bismuth orthophosphate (IV, 17E) ;
(c) aluminium as the basic benzoate and subsequent ignition to
the oxide (IV, 28C) ;
(d) ferric iron as the oxinate (IV, 31C) ;
(e) nickel as the dicyandiamidine complex (IV, 32D) ;
(f) cobalt as the a-nitroso-~-naphthol complex and weighing as
cobalt sulphate or as metallic cobalt (IV, 33A); and
(g) thorium as thorium iodate (IV, 38C).
Sections IV, 77-86 (Electrolytic Determinations) have been con-
siderably revised. Sections IV, 87-89 deal with Depositions with
Controlled Potential at the Cathode, and full details are given, inter
alia, for the construction of an apparatus for automatic control of the
cathode potential. Extensive changes have been made in Section
IV, 96 (Analysis of Steel).
Chapter V (COLORIMETRIC ANALYSIS-SPECTROPHOTOMETRY- TURBIDI-
METRY AND NEPHELOMETRY-FLUORIMETRY).
This Chapter has been enlarged by the incorporation of accounts of
more recent apparatus; several new determinations have been added.
Chapter VI (POTENTIOMETRIC TITRATION METHODS), Chapter VII (CON-
DUCTOMETRIC TITRATION METHODS), Chapter VIII (POLAROGRAPHY), and
Chapter IX (AMPEROMETRIC TITRATIONS) are new. Attention is directed
to the details for the construction of a polarograph in Chapter VIII.
Chapter IX (GAS ANALYSIS) remains substantially unchanged. It was
felt that a comprehensive text-book should contain an account of micro-
analysis. A new Chapter XI (MICRO-GRAVIMETRIC AND MICRO-
VOLUMETRIC ANALYSIS) has accordingly been included, and it is hoped
that this will provide a useful introduction to this important subject.
It is impossible to make adequate acknowledgment to all who have
contributed either directly or indirectly to the present volume. Com-
mercial firms and organisations have always been willing to help in
providing diagrams, descriptive literature, and special information, and
VUI Preface to Second Edition
the names of these firms are given in the appropriate sections of the
text. The author wishes to place on record the debt he owes to these
firms and organisations, and takes this opportunity of thanking them
for their assistance. In connexion with the experimental work, he
is indebted to a number of undergraduates and staff (both laboratory
and teaching) of the Chemistry Department of this Polytechnic.
Especial thanks are due to :
(i) H. E. Akerman and D. G. H. Ballard for their work with
dicyandiamidine sulphate as a reagent for nickel.
(ii) C. M. Ellis, B.Sc., for checking and developing many of
the determinations involving instrumental methods of analysis
(potentiometric titrations, polarography, and amperometric titra-
tions) and also for his experiments on vanadous sulphate
solutions.
(iii) J. Leicester, M.Sc., F.R.I.C., for checking many of the new
volumetric and some gravimetric procedures.
(iv) J. Palmer and C. Wadsworth for the construction of the
polarograph and the apparatus for the automatic control of the
potential at the cathode.
(v) J. Palmer and J. Watling for assistance in the preparation
of many of the new diagrams.
(vi) C. M. Ellis, J. Leicester, and Dr. G. H. Jeffery for reading
all the galley proofs and making a number of helpful suggestions.
(vii) Dr. G. H. Jeffery, F.R.I.C., for his assistance in a super-
visory capacity in numerous ways; his advice upon many matters
of detail has led to the elimination of much ambiguity.
I must acknowledge my indebtedness to Dr. A. Claassen of Eind-
hoven, Holland, who has given me the benefit of his wide experience
and has also made a number of suggestions for new procedures which
have been used.
The author would appreciate constructive suggestions for the
improvement of the book and also to have his attention drawn to any
errors which may have escaped his notice.
ARTHUR I. VOGEL
Woolwich Polytechnic, London, S.E.1S.
January, 1951.
PREFACE TO FIRST EDITION
IN writing this book, the author had as his primary object the provision
of a complete up-to-date text-book of quantitative inorganic analysis,
both theory and practice, at a moderate price to meet the requirements
of University and College students of all grades. It is believed that
the material contained therein is sufficiently comprehensive to cover
the syllabuses of all examinations in which quantitative inorganic
analysis plays a part. The elementary student has been provided for,
and those sections devoted to his needs have been treated in consider-
able detail. The volume should therefore be of value to the student
throughout the whole of his career. The book will be suitable inter alia
for students preparing for the various Intermediate B.Sc. and Higher
School Certificate Examinations, the Ordinary and Higher National
Certificates in Chemistry, the Honours and Special B.Sc. of the Uni-
versities, the Associateship of the Institute of Chemistry, and other
examinations of equivalent standard. It is hoped, also, that the wide
range of subjects discussed within its covers will result in the volume
having a special appeal to practising analytical chemists and to all
those workers in industry and research who have occasion to utilise
methods of inorganic quantitative analysis.
The kind reception accorded to the author's Text Book of Qualitative
Chemical Analysis by teachers and reviewers seems to indicate that
the general arrangement of that book has met with approval.' The
companion volume on Q7Lantitative Inorganic Analysis follows essentially
similar lines. Chapter I is devoted to the theoretical basis of quantita-
tive inorganic analysis, Chapter II to the experimental technique of
quantitative analysis, Chapter III to volumetric analysis, Chapter IV
to gravimetric analysis (including electro-analysis), Chapter V to
colorimetric analysis, and Chapter VI to gas analysis; a comprehensive
Appendix has been added, which contains much useful matter for the
practising analytical chemist. The experimental side is based essenti-
ally upon the writer's experience with large classes of students of
various grades. Most of the determinations have been tested out in
the laboratory in collaboration with the author's colleagues and senior
students, and in some cases this has resulted in slight modifications
of the details given by the original authors. Particular emphasis
has been laid upon recent developments in experimental technique.
Frequently the source of certain apparatus or chemicals has been given
in the text; this is not intended to convey the impression that these
materials cannot be obtained from other sources, but merely to indicate
that the author's own experience is confined to the particular products
mentioned.
The ground covered by the book can best to judged by perusal of
the Table of Contents. An attempt has been made to strike a balance
between the classical and modern procedures, and to present the
subject of analytical chemistry as it is to-day. The theoretical aspect
ix
x Preface to First Edition
has been stressed throughout, and numerous cross-references are given
to Chapter I (the theoretical basis of quantitative inorganic analysis).
No references to the original literature are given in the text. This
is because the introduction of such references would have considerably
increased the size and therefore the price of the book. However, a
discussion on the literature of analytical chemistry is given in the
Appendix (Section A, 3). With the aid of the various volumes
mentioned therein-which should be available in all libraries of
analytical chemistry-and the Collective Indexes of Chemical Abstracts
or of British Chemical Abstracts, little difficulty will, in general, be
experienced in finding the original sources of most of the determinations.
described in the book.
In the preparation of this volume, the author has utilised pertinent
material wherever it was to be found. While it is impossible to
acknowledge every source individually (see, for example, Section A, 3),
mention must, however, be made of Hillebrand and Lundell's Applied
Inorganic Analysis (1929) and of Mitchell and Ward's Modern Methods
in Quantitative Chemical Analysis (1932). In conclusion, the writer
wishes to express his thanks: to Dr. G. H. Jeffery, A.LC., for reading
the galley proofs and making numerous helpful suggestions; to Mr.
A. S. Nickelson, RSc., for reading some of the galley proofs; to his
laboratory steward, Mr. F. Mathie, for preparing a number of the
diagrams, including most of those in Chapter VI, and for his assistance
in other ways; to Messrs. A. Gallenkamp and Co., Ltd., of London,
E.C.2, and to Messrs. Fisher Scientific Co., of Pittsburgh, Pa., for
providing a number of diagrams and blocks; * and to Mr. F. W.
Clifford, F.L.A., Librarian to the Chemical Society, and his able
assistants for their help in the task of searching the extensive literature.
Any suggestions for improving the book will be gratefully received
by the author.
Woolwich Polytechnic, London, S.E.lS.
June, 1939.
* Acknowledgment to other firms and individuals is made in the body of the text.
CONTENTS
CHAPTER I
THE THEORETICAL BASIS OF QUANTITATIVE INORGANIC
ANALYSIS
PAGE
I, 1. Electrolytic dissociation 1
I, 2. The law of mass action . . . . . . . 3
I, 3. Application of the law of mass action to solutions of electrolytes 4
I, 4. Strengths of acids and bases . . . . . . 5
I, 5. Activity and activity coefficient 6
I, 6. Ionisation of polybasic acids 8
1, '7. Common ion ~{f~ct . Q
I, 8. Solubility product . . . 11
I, 9. Completeness of precipitation. Quantitative effects of a
common ion. . . . . . 14
I, 10. Limitations of the solubility product principle 15
I, 11. Fractional precipitation . . . . 17
I, 12. Complex ions . . . . ' 18
I, 13. Effect of acids upon the solubility of a precipitate . 20
I, 14. Effect of temperature upon the solubility of a precipitate 21
I, 15. Effect of the solvent upon the solubility of a precipitate 22
1. 16. The ionic product of water . 22
1,17. The hydrogen-ion exp'onent, pH . 23
I, 18. The hydrolysis of salts . . . . 25
I, 19. HydTolysis constant and degree of hydrolysis . 27
I, ZO. Buffer solutions . 30
VOLUMETRIC ANALYSIS
I, 21.
Volumetric analysis . . . . . 35
I, Classification of reactions in volumetric analysis
22. 36
I, 23.
Equivalent weights. Normal solutions. . 36
I, 24.
Advantages of the use of the equiv&lent system for the prepara-
tion of standard solutions . . . . . . . 43
I, 25. Preparation of standard solutions . 45
I, 26. Primary standard substances 46
THEORY OF ACIDIMETRY AND ALKALIMETRY
I, 27. Neutralisation indicators . . 47
I, 28. Preparation of indicator solutions . 53
I, 29. Mixed indicators. . . . 55
I, 30. Universal or multiple range indicators 56
I, 31. Neutralisation curves. . . 57
I, 32. Neutralisation of a strong acid and a strong base 57
I, 33. Neutralisation of a weak acid with a strong base 60
I, 34. Neutralisation of a weak base with a strong acid 62
I, 35. Neutralisation of a weak acid with a weak base 63
I, 36. Neutralisation of a polybasic acid with a strong base . . 64
I, 37. Titration of solutions of hydrolysed salts. Displacement
titration . . . . . 66
I, 38. Choice of indicators in neutralisation reactions 68
xi
xii Contents
ELECTRO-ANALYTICAL METHODS
I, 64. Theory of electro-analysis 128
I. 65. Decomposition potential 129
I. 66. Electrode reactions 131
I, 67. Overvoltage 132
I, 68. Completeness of deposition 132
I. 69. Electrolytic separation of metals 134
I. 70. Character of the deposit 135'
I, 71. Electrolytic separation of metals with controlled cathode potential 136
I. 72. Internal electrolysis 138
I. 73. Separation by miscellaneous physical methods 139
I. 74. Errors in quantitative analysis 142
I. 75. Classification of errors. 143
I, 76. Minimisation of errors . 146
1,77. Significant figures and computations . 147
I, 78. Selected bibliography on the theory of gravimetric analysis,
organic reagents, electro-analysis and related subjects. 149
Contents xiii
CHAPTER II
MISCELLANEOUS OPERATIONS
II, 39. Reduction with metals . 222
II, 40. Selected bibliography on technique of quantitative analysis 226
xiv Contents
CHAPTER III
VOLUMETRIC ANALYSIS
ACIDIMETRY AND ALKALIMETRY
PAGE
CHAPTER IV
GRAVIMETRIC ANALYSIS
IV, 1. General discussion 397
IV, 2. Note-book, entries, and calculations 397
IV, 3. Calculations of gravimetric analysis. Chemical factors. 397
xviii Contents
PAGE
IV, 9. D. of aluminium as aluminium oxide 410
IV, 10. D. of calcium as oxalate . . 411
IV,l1. D. of magnesium as the ammonium phosphate hexahydrate
and as the pyrophosphate 414
IV, 12. D. of nickel as the dimethylglyoxime complex 417
SYSTEMATIC GRAVIMETRIC ANALYSIS
IV, 13. General discussion 419
IV,14. Lead 420
IV, 15. Silver 422
IV,16. Mercury
IV, 17. Bismuth
423
425
...
IV,18. Cadmium. 427
IV,19. Copper 430
IV, 20. Arsenic 433
IV,21. Antimony 435
IV,22. Tin . 437
IV, 23. Molybdenum . 439
IV,24. Selenium and tellurium 441
IV,25. Platinum. 443
IV, 26. Palladium 444
IV, 27. Gold 445
IV,28. Aluminium 447
IV, 29. Beryllium 450
IV,30. Chromium 452
IV, 31. Iron 455
IV, 32. Nickel 457
IV, 33. Cobalt 461
IV,34. Zinc 463
IV,35. Manganese 468
IV,36. Vanadium 469
IV, 37. Uranium . 470
IV,38. Thorium . 471
IV,39. Cerium 473
IV, 40. Titanium . 473
IV, 41. Zirconium 475
IV,42. Thallium . 477
IV,43. Calcium 478
IV, 44. Strontium 479
IV,45. Barium 479
IV,46. Magnesium 481
IV, 47. Sodium 482
IV,48. Potassium 484
IV, 49. Lithium . 490
IV,50. Ammonium 49l
IV, 51. Tungsten. 491
IV, 52. Chloride . 492
IV, 53. Bromide . 493
IV, 54. Iodide 493
IV, 55. Thiocyanate 493
IV, 56. Cyanide 494
IV, 57. Fluoride . 494
IV, 58. Chlorate . 496
IV, 59. Perchlorate 496
IV,60. Iodate 497
Contents XIX
PAGE
ELECTROLYTIC DETERMINATIONS
IV, 77. Apparatus 509
IV, 78. Copper . 518
IV, 79. Lead . 520
IV, 80. Cadmium 522
IV, 81. Nickel 523
IV, 82. Cobalt 524
IV, 83. Silver 524
IV, 84. Zinc . 524
IV, 85. Bismuth. . . . . . . . . . 525
IV, 86. Electrolytic separation and determing,tion of copper and nickel 526
CHAPTER V
COLORIMETRIC ANALYSIS-SPECTROPHOTOMETRY-TURBIDI.
METRY AND NEPHELOMETRY-FLUORIMETRY
PAGE
CHAPTER VI
CHAPTER VII
CHAPTER VIII
POLAROGRAPHY
CHAPTER IX
AMPEROMETRIC TITRATION'S
CHAPTER X
GAS ANALYSIS
pAGE
CHAPTER XI
APPENDIX J
A, International atomic weights, 1949
1. 841
A, 2.
Chemical factors. . . . 842
A, 3.
The literature of analytical chemistry 845
A, 4.
Densities of acids at 20 C.. . 851
A, 5.
Densities of alkaline solutions at 20 C. 853
A, 6.
Data on the strength of aqueous solutions of the common acids
and of ammonium hydroxide . 853
A, 7. Samples and solutions for elementary analysis 854
A,8. Analysed samples . . 855
A, 9. Solubilities of some inorganic compounds in water at various
temperatures 866
Oontent.s XXlll
PAGE
Index 905
CHAPTER I
THE THEORETICAL BASIS OF QUANTITATIVE INORGANIC
ANALYSIS
I, 1. Electrolytic dissociation.-Many of the reactions of qualitative
and quantitative analysis take place in aqueous solution. It is there-
fore necessary to have a general knowledge of the conditions which
exist in such solutions. It is assumed that the reader is familiar with
the broad concepts of the simple theory of electrolytic dissociation.
Ionisation of acids and bases in solution. An acid may be defined as a
substance which, when dissolved in water, undergoes dissociation with
the formation of hydrogen ions as the only positive ion:
HCI ~ H+ + 01-
HN0 3 ~ H+ + N0 3-
Actually the free hydrogen ions H+ (or protons) do not exist in the
free state in aqueous solution; each hydrogen ion combines with one
molecule of water to form the hydroxonium ion H30+. The hydroxon-
ium ion is a hydrated proton. The above equations are therefore more
accurately written :
HOI + H 2 0 ~ H30+ + 01-
HN0 3 + H 2 0 ~ H30+ + N0 3-
The ionisation may be attributed to the great tendency of the free
hydrogen ions H+ or protons to combine with water molecules to form
hydroxonium ions. Hydrochloric and nitric acids are almost com-
pletely dissociated in aqueous solution in accordance with the above
equations; this is readily detected by freezing-point measurements and
bv other methods .
Polybasic acids ionise in stages. In sulphuric acid, the first hydrogen
atom is almost completely ionised:
H 2S0 4 ~ H+ + HS0 4-
or H 2S0 4 + H 2 0 ~ H30+ + HS0 4 -
The second hydrogen atom is only partially ionised, except in very dilute
solution:
HS0 4- ~ He + S04--
or HS0 4 - + H 20 ~ H30+ + S04--
Phosphoric acid also ionises in stages:
H 3P0 4 ~ H+ + H 2P0 4 - ~ H+ + HP0 4-- ~ H+ + P0 4- - -
Acid. Base.
CHaCOOH ~ H+ + CH 3COO-
HCl~H++Cl-
NH4+ ~ H+ + NH3
H 2P0 4- ~ H+ + HP0 4 - -
* For a detailed account, see, for example, 'V. F. Luder and S. Zuffani, Electronic
Theory of Aci<lB and Bases. J. Wiley: Chapman and Hall. 1946.
The Theoretical Basis of Quantitative Analysis 3
Acid. Base.
AI(H 20)6+++ ~ Hl- + AI(H 20hOH ++
HaO+ ~ H+ + H 2 0
H 20 ~ H+ + OH-
Attention is drawn to the duality in acid-base systems in which each
acid has a conjugated base related to it. The interaction of an acid
Al of one system with a base B2 of another system, i.e., the acid-base
reaction, may be written:
Acid l (Al) ~ Basel (B l ) + Proton
+
Acid 2 (A 2 ) ~ Base 2 (B 2 ) Proton
or Al +
B2 ~ A2 + Bl
Thus HCI + H 20 ~ HaO+ + CI-
NH/ + CHaCOO- ~ CHaCOOH + NHa
Salts. The structure of numerous salts in the solid state has been
investigated by means of X-rays and by other m0thods, and it has been
shown that they are compos~d of charged atoms or groups of atoms
held together in a crystal lattice. When these salts are dissolved in a
solvent of high dielectric constant such as water, or are heated to the
melting point, the crystal forces are weakened and the substances
dissociate into the pre-existing charged particles or ions, so that the
resultant liquids are good conductors of electricity. The complete
dissociation of salts in aqueous solution is the modern view, and is
now almost universally accepted. There are, however, some exceptions,
and these have, in some cases, been supported by X-ray measurements.
Feebly ionised salts (weak electrolytes) are exemplified by the cyanides,
thiocyanates, and halides of mercury and cadmium, and by lead acetate.
The theoretical implications of the theory of complete ionisation,
due to Debye, Huckel, and Onsager, have been fully worked out by these
authors. In particular, they have been able to account for the increas-
ing equivalent conductance with decreasing concentration over the
concentration range O-O002N. For full details the reader must be
referred to text-books of physical chemistry; a short account will be
found in the author's Text Book of Qualitative Chemical Analysis (Third
Edition, 1945).
It is import"~t, to realise that whilst complete ionisation occurs with
strong electro~J s, this does not mean that the effective concentrations of
the ions are the same at all concentrations, for if this were the case, the
osmotic properties of aqueous solutions could not be accounted for.
The variation of osmotic properties is ascribed to changes of the
activity of the ions; these are dependent upon the electrical forces
between the ions. Expressions for the variations of the activity
or of related quantities, applicable to dilute solutions, have also been
deduced by the Debye-Huckel-Onsager theory. Further considera-
tion of the concept of activity will be found in Section I, 5.
or [0] X [D] = ~ = K
[A] X (B] k2
\
K is the equilibrium constant of the reaction at the giVen temperature.
The expression may be geneIalised. For a reversible reaction
represented by :
PIAL + pzAz + P3 A 3 + .... ~ qlB l + qzB z + q:JB3 + ....
where Pl' P2' P3 and ql> q2' q3 are the number of molecules of reacting
substances, the condition for equilibrium is given by the expression:
[B 1}11 X (B 21q, X [B31-:_'__._. . = K
[A1]Pl X [A 21P, X [A 3}l" . . .
#
This is the rigorously correct expression for the law of mass action as
applied to weak electrolytes. .
The activity coefficient varies with the concentration. For ions
it varies with the valency, and is the same for all dilute solutions having
the same ionic strength, the latter being a measure of the electrical field
existing in the solution. The term ionic strength, designated by the
symbol/L, was introduced by Lewis and Randall in 1921, and is defined
as equal to one half of the sum of the products of the concentration of
each ion multiplied by the square of its valency, or /L = O5~CiZi2,
where Ci is the ionic concentration in gram-molecules per litre of solution
The Theoretical Basis of Quantitative Analysis
TABLE n.-DISSOCIATION CONSTANTS AT 25 C.
I
Succinic
- H 2 'C 4H 4 0 4
/(2 80
/(1 663
X
X
10-6
10- 5 t
510
418
/(2 254 X 10-6 t 560
Sulphuric H 2 'SO, /(z 115 X 10-2 t .1'94,
Sulphurous Hz'SO s K1 17 X 10-2 177,
K2 50 X 10-6 530 .
dTartaric H 2 'C4H 4 0 6 K1 104 X lO-s t 298
K2 455 X 10-5 t 434
Boric H'H 2 BO a K1 580 X 10-10 t 924
Solubility Solubility
Substance. Product. pS. Substance. Product. pS
...
BaCI Z
c~ic...... ____________ !_{_I
O~-O-.~02---0.~04---0.~06---0~0-8--0.~10---0~.12---0~.14--0~16
Normality of added salt
80r------------------,
'"~ 70
x
""v
"" 40
~
""
~30
50;- added
(Calc.)
;:"
~ 20 AgN0 3
""'" 10 .. -_~_~_...__~,_j
" . Ag+ added
(Cald
o 002 004 006 008 010
Normality 0/ added salt
FIG. I, 10, 2.-Influence of Various Salts on the Solubility of AgzSO,.
removed from unity, and the expression (1) reduces to the classical
solubility product equation.
Numerous experiments have been carried out to determine the
accuracy with which the solubility product principle applies. Some
results of Bray and Winninghoff (1911) upon the solubility of thallous
chloride in the presence of various salts are shown in Fig. 1,10,1. The
dotted line represents the effect of a simple uni-univalent salt with a
common ion, calculated by assuming complete dissociation of the salt.
The salts with a common ion decrease the solubility to nearly the same
extent, and are in approximate agreement with the values computed
on the basis of the simple solubility product principle. Fig. I, 10, 2
The Theoretical Basis of Quantitative Analysis 17
shows graphically some selected results for silver sulphate. The
addition, in moderate concentrations, of a common univalent ion, like
Ag+, is in approximate agreement with the simple theory, but no such
agreement is obtained by the addition of a common divalent ion, like
SO 4- -. A striking fact that emerges from these studies is that the
solubility increases in most cases upon the addition of electrolytes with
no common ion; we may term this influence the salt effect. Further-
more, it was found that the salt effect depends upon the valency of the
ions of the precipitate and upon the nature of the added electrolyte;
usually it increases markedly with increasing valency of the ions of the
precipitate. The addition of a salt with no common ion will increase
the ionic strength of the solution and hence decrease the activity
coefficients of both ions of the sparingly soluble salt; the solubility
of the latter must increase in order that the activity product,
[M+]. [A-] .JM+ .jA-' may be kept constant. It can be shown on the
basis of the Debye-Huckel-Onsager theory that for aqueous solutions
at 25 C. :
0505z i 2 fL0.5
10gJi = - 1 +
3.3 X 107a. fLo. s
(3)
and (4)
I
Hence when the concentration of the iodide ion is about one millionth
part of the chloride-ion concentration, silver chloride will be precipi-
tated. If the initial concentration of both chloride and iodide ions is
OlN, then silver chloride will be precipitated when
where ax, [x], and fx refer to the activity, concentration, and activity
coefficient of the species x. Since water is only slightly ionised, the
ionic concentrations will be small, and their activity coefficients may be
regarded as unity; the activity of the unionised molecules may also be
taken as unity. The expression thus becomes:
[H+] X [OH-] = a constant
[H 20]
In pure water or in dilute aqueom~ solutions, the concentration (if the
undissociated water may be considered constant. Hence:
[H+] X [OH-] = Kw
where Kw is the ionic product of water. It must be pointed out that the
assumption that the activity coefficients of the ions are unity and that
that activity coefficient of water is constant applies strictly to pure water
and to very dilute solutions (ionic strength < 0'01); in more conceni ,
trated solutions, i.e., in solutions of appreciable ionic strength, the
electrical environment affects the activity coefficients of the ions
(compare Section I, 10) and also the activity of the unionised water.
The ionic product of water will then not be constant, but will depend
upon the ionic environment. It is, however, difficult to determine the
activity coefficients, except under specially selected conditions, so that
in practice the ionic product K w , although not strictly constant, is
employed.
The ionic product varies with the temperature, but under ordinary
experimental conditions (at about 25 C.) its value may be taken as
1 X 10-14 with concentrations expressed in gram-ions per litre. This is
sensibly constant in dilute aqueous solutions. If the product of [H+]
and [OH-] in aqueous solution momentarily exceeds this value, the
* Strictly speaking the hydrogen ion H+ exists in water as the hydroxonium ion
H30+. The electrolytic dissociation of water should therefore be written:
2H 20 ~ HaO+ + OH-
For the sake of simplicity, the more familiar symbol H+- will be retained.
The Theoretical Basis of Quantitative Analysis 23
excess ions will immediately combine to form water. Similarly, if the
product of the two ionic concentrations is momentarily less than 10-14 ,
more water molecules will dissociate until the equilibrium value is
attained.
The hydrogen- and hydroxyl-ion concentrations are equal in pure
water; therefore [H+] = [OH-] = ~ = 10-7 g.-ions per litre at
about 25 C. A solution in which the hydrogen- and hydroxyl-ion
concentrations are equal is termed an exactly neutral solution. If
[H+] is greater than 10-7 , the solution is acid, and if less than 10-7 , the
solution is alkaline (or basic). It follows that at ordinary temperatures
[OH-] is greater than 10-7 in alkaline solution and less than this value
in acid solution.
In all cases the reaction of the solution can be quantitatively ex-
pressed by the magnitude of the hydrogen-ion (or hydroxonium-ion)
concentration, or, less frequently, of the hydroxyl-ion concentration,
since the following simple relations between [H+] and [OH-] exist:
[H +J - Kw
, - [OH-], an
d [OH-] _ Kw
- [H+]
The variation of Kw with temperature is shown in Table VI.
TABLE Vr.-IONIC PRODUCT OF WATER AT VARIOUS TEMPERATURES
i ; ; I";""'j " i
1610 1011 1612 1013 1014
4 5 6 7 9
[H+] 1(1c) 1()1 10 10 10 16 10 10 lOB 10
pH r Ii;
pOH 14 ,3 '2 " '0 {) 8 7 6 5 4 3 2 0
14 13 12 10 9 7 6 5 4 3 2 1
[Otl-] 10 10 10 1011 10 10 lOB 10 10 10 10 10 10 16 1(10")
This equation can also be obtained by combining (1) and (2), since both
equilibria must co-exist.
This interaction between the ion (or ions) of a salt and the ions of
water is called hydrolysis. Formerly the chemical reaction was written:
MA + H 0 ~ MOR + HA
2
This is a quadratic equation for [H+] and may be solved in the usual
manner. It can, however, be simplified by introducing the following
further approximations. In a mixture of a weak acid and its salt, the
dissociation of the acid is repressed by the common ion effect, and
[H+] may be taken as negligibly small by comparison with Ca and cs
Equation (3) then reduces to :
[H +] -- C;'
Ca K
a, 01
. [H+] - [Acid]
- [StLlt] X
K
a
(4)
or p H -- p K a + Iog [ACId]
.
[Salt] (5)
32 Quantitative Inorganic Analysis
Similarly for a mixture of a weak base of dissociation constant Kb
and its salt with a strong acid :
- [Base]
[OH ] = [Saltf X Kb (6)
[Salt]
or pOH = pKb + log [Acid] (7)
only upon the ratio of the concentrations of acid and salt and upon K a ,
and not upon the actual concentrations; otherwise expressed, that
the pH of such a buffer mixture should not change upon dilution with
water. This is approximately although not strictly true. In deducing
equation (2), concentrations have been substituted for activities, a
step which is not entirely justifiable except in dilute solutions.
Theoretically, the expression controlling buffer action is :
(8)
OXIDANTS
Potassium pennang<tnate (acid) Mn0 4- + SH+ + 5. ~ Mn++ + 4H 20
Potassium permanganate
(neutral) . Mn0 + 2H 0 + 3. ~ MnO a + 40H-
4- 2
Potassium permanganate
(strongly alkaline) Mn0 + ~ Mn0 4- 4--
Ceric sulphate Ce++++ + ~ Ce+++
Potassium dichromate Cr 0
2 7--+ 14H+ + 6. ~ 2Cr+++ + 7HaO
Chlorine CIa + 2. ~ 2C1-
Bromine Br2 + 2. ~ 2Br-
Iodine. Ia + 2. ~ 21-
Ferric chloride Fe+++ + ~ Fe H '
Potassium bromate BrO a- + oH+ + o. ~ Br- + 3H aO
Potassium iodate . 10 + 6H+ + 8. ~ 1- + 3HaO
3-
Sodium hypochlorite CI0- + H 0 + 2. ~ Cl- + 20H-
2
Hydrogen peroxide H 0 a + 2H+ + 2. ~ 2HaO
2
Manganese dioxide Mn0 + 4H+ + 2. ~ Mn + 2H 0
2
H
2
Sodium bismuthate Bi0 + 6H+ + 2. ~ Bi+++ + 3HaO
3-
Nitric acid (cone.) N0 + 2H+ + .~N02 + H 20
3-
Nitric acid (dilute) N0 + 4H+ + 3. ~ NO + 2H 0
3- 2
REDUCTANTS
Hydrogen H2 - 2.~ 2H+
Zinc . . Zn - 2. ~ ZnH
Hydrogen sulphide Has - 2. ~ 2H+ + 8
Hydrogen iodide 2HI - 2. ~ 12 + 2H +
Oxalic acid. . C2 0 4-- - 2. ~ 2C02
Ferrous sulphate . Fe++ - ~ Fe+++
Sulphurous acid H.SOa + H 2 0 - 2. ~ S04-- + 4H+
Sodium thiosulphate 2S a0 3 -- - 2. ~ 8 4 0 6 --
Titanous sulphate Ti+++ - ~ Ti++++
Stannous chloride. Sn H - 2. ~ Sn+HI-
Stannous chloride (in presence
of hydrochloric acid) .' I' SnH + 6Cl- - 2. ~ SnC1 6 --
JIydrogen peroxide H 20 2 - 2.~ 2H+ + O2
Substance.
Radical
or
O.N. of
" Effec- ReductiO: l~Yew--,----cr-~-~-~e~-iJ~-;l~;-
Element tive" Product. 0.11'. in trons.
int'olt'ed. Element. O.N.
r------~-----I--------I------I-
KMnO~ (acid) +7 Mn++ +2 5 5
KMn0 4 (neutral) +7 Mn0 2 or +4 3 3
J\ln\ ~H
KMn0 4 (strongly
alkaline) Mn0 4- +7 Mn0 4-- +6 1 1
K 2 Cr 2 0 7 Cr 2 0 7-- +6 Cr!-H +3 3 3
H~Oa (dil.) NO a- +5 NO +2 3 3
HN0 3 (cone.) NO a- +5 K0 2 +4 1 1
Cl, Cl o CI- -1 1 1
Br2 Er G Er- -1 1 1
12 I o 1- -1 1 1
3HCl: IHN0 3 CI o Cl- -1 1 1
H 20 2 o o 0-- -2 2 2
Na 2 0 2 o o 0-- -2 2 2
KCIO a CIO a- +5 CI- -1 6 6
KBrOa ErO a- +5 Br -1 6 6
KIO a IO a- +5 1- -1 6 6
NaOCI OCl- +1 Cl- -1 2 2
FeCl a Fe+++ +3 Fe++ +2 1 1
Ce(80 4 )2 Ce+++!- +4 I Ce+++ +3 1 1
The actual colour of the indicator, which depends upon the ratio of
the concentrations of the ionised and unionised forms, is thus directly
related to the hydrogen-ion concentration. Equation (3') (the
simplified or " classical" form) may be written logarithmically;
[In-]
pH = log [HIn] pKina + (4)
. OH 0 0
Colourless (lactone) Red (quinone) Red
(pseudo acid) (acid) (salt or ion)
HIn' ~ HID F la- +fi+
FIG. I, 27, 1.
,automeric forms possessing different constitutional formulffi and
lifferent colours; one of the forms is a non-electrolyte (a pseudo-acid or
~seudo-base), the other form being an acid or a base. The ions of the
erue acid or true base possess the same colour as the undissociated form of
;he same structure. We can illustrate this by reference to phenol-
phthalein, the changes for which are characteristic of all phthalein
indicators (Fig. I, 27, 1).
The Theoretical.Basis of Quantitative Analysis 49
In the solid state or in acid solution, it exists chiefly as the colourless
lactone I. This is in equilibrium in solution with a trace of the tauto-
meric quinonoid form II, *. which is an acid since it possesses the
carboxyl group -COOH and dissociates to yield the H+ ion and the
indicator ion III.
Consider now an acid or, more correctly, a pseudo-acid indicator in
the light of the new theory. Let HIn' represent the pseudo-acid and
BIn the acid. Two equilibria must be considered in aqueous solution;
HIn' ~ HIn . (7)
and HIn ~ H+ + In- . (H)
Applying the law of mass action to both, we have:
for (7), KT = aRInlallIn' (9)
and for (8), KI = ail+ X aIn- laRIn ( 10)
The ion In- has the same colour as the weak acid HIn. In acid solution,
i.e., in the presence of excess of H+ ions, the indicator will exist largely
as HIn and HIn'. Now these two forms have different colours, and
HIn has the same colour as In-. The indicator will only be useful if
the equilibrium constant for the tautomeric equilibrium (7) is very
small; then practically the whole of the undissociated indicator will
be in the form HIn' . Combining (9) and (10), we obtain :
* The change from the benzenoi.d to the quinonoid form is believed to be responsible
for the production of colour :
I I I I
#O-O~ 0==0
-0/ '0- --+ =0/ "0=
"0=0/ "C=C/
I I I I
or more probably a state of resonance or mesomerism obtains wherein the coloured ion
possesses a structure intermediate between the various possible benzenoid and quinonoid
forms.
50 Quantitative Inorganic A nalysi~
If the activity coefficient of the in~icator anion may be expressed
by the usual equation (Section '1, 20), It follows that:
pH = pKiua + log [Iri-]j[HIn'] - O505zi 2p O.5 + Op- (13')
In dilute solution (fL i> 0'01) the term Op may be neglected, and the
equation reduces to :
pH = pKina + log [In-lIlH1n') - 0505zi 2p-0 'r, (13")
The colour of an indicator is determined by the ratio of the concen-
trations of HIn' and In- (the pseudo-acid and the ionised form), but the
actual pH will depend upon the ionic strength of the solution (equation
13"). Hence when making a colour comparison for the determination
of the pH of a solution not only must the indicator concentration be the
same in the two solutions, but, the ionic strengths must be equal or
approximately equal. Equations (13') and (13") incidentally provide
an explanation of the so-called" salt effect" which is observed with
indicators.
For many practical purposes it is sufficient to write equation (13')
ln the form:
pH = pKina +
log [In-]/[HIn'] ( 13'")
provided the influence of ionic strength be borne in mind. As alrel,ldy
mentioned, the colour of an indicator is determined by the ratio of
the concentrations of the "acid" and " alkaline" forms. Both forms
are present at any hydrogen-ion concentration. It must be realised,
however, that the human eye has a limited ability to detect either of
the two colours when one of them predominates. Experience shows
that the solution will appear to have the" acid" colour, i.e., of Hln',
when the ratio of [HIn') to [In-] is above approximately 10, and the
" alkaline" colour, i.e., of In-, above a similar ratio of [In-) to [HIn') of
approximately 10. Thus only the" acid" colour will be visible when
[HIn'JI[ln-) > 10, the corresponding limit of pH given by equation
(13'1f) is :
pH =pKina-1
only the "alkaline" colour will be visible when [In-l/[Hln'l > 10,
and the corresponding limit of pH is :
pH = pKina +1
The colour-change interval is accordingly pH = pKina 1, i.e., over
approximately two pH units. Within this range the indicator will
appear to change from one colour to the other. The change will be
gradual, since it depends upon the ratio of the concentrations of the
two coloured forms (pseudo-acid and ionised). When the pH of the
solution is equal to the apparent dissociation constant of the indicator
pKina , the ratio [Hln'] to [In-] becomes equal to 1, and the indicator
will have a colour due to an equal mixture ofthe " acid" and" alkaline"
forms. This is sometimes known as the middle tint of the indicator.
This applies strictly only if the two colours are of equal intensity. If
one form is more intenselv coloured than the other or if the eye is more
sensitive to one I ANGRAU Central Library 1 the middle tint will be
slightly displaced Hyderabad indicator.
1060
!~I!I! !!I!! 11!l11!!!! 111111
The Theoretical Basis of Quantitative Analysis 51
For an indicator base we have, according to the modified theory, the
two equilibria:
In'OH ~ InOH . (14)
and InOH ~ 1n+ OH- . + (15)
The following equation may be deduced along similar lines to that
described for an indicator acid:
.f -[OH-] = [In'OH] K. jln'OR
JOR [In'] X mb X fru+
The equation is of the same form as (12), since the ratio of the two
constants may be replaced by a new constant K inb,.
The above theory applies only to a monobasic acid or to a monoacid
base. Complications arise if two such changes are possible, and the
transition range may be increased.
The apparent ionisation constant of an indicator may be determined
approximately by finding either the pH of a solution (Section I, 17)
containing it when it shows its middle tint, or by finding the range of
hydrogen-ion concentration in which definite colour changes are ob-
served; the pH of such a solution lies within the limits pKina (or
pKinb ) 1. A more accurate method depends upon the determination
of the fraction of the indicator (e.g., [In-])Hln')) which has changed
colour in a series of solutions of known pH (buffer solutions-Section
I, 20); the approximate apparent dissociation constants may then be
calculated from equations (12) or (17), the activity coefficients being
assumed to be unity. With a one-colour indicator the colour intensity
is measured, e.g., by means of a colorimetric or spectrophotometric
method, in a series of solutions of equal concentration of indicator and
different values of pH. For an indicator of the phenolphthalein type,
the standard of comparii'lon will be a solution containing an appreciable
excess of alkali: this will correspond to a value of [In-] equal to the
total indicator concentration. With a two-colour indicator, various
modifications must be introduced, which cannot, however, be discussed
here. In some cases, e.g., p-nitrophenol and methyl orange, the con-
stants may be determined by conductance measurements or by a, study
of the hydrolysis of salts. Some approximate values of the apparent
dissociation constants of indicators, which we may term indicator
constants Kin, are given in Table X. This Table contains a selected
list of indicators suitable for volumetric analysis and also for the
colorimetric determination of pH (Section V, 9).
It is necessary to draw attention to the pH of various types of water
which may be encountered in quantitative analysis. Water in equili-
brium with the normal atmosphere containing 003 per cent by volume
of carbon dioxide has a pH of about 57; very carefully prepared
conductivity water has a pH close to 7; water saturated with carbon
52 Q'uant'itative Inorganic Analysis
TABLE X.-COLOUR CHANGES AND pH RANGE OF CERTAIN INDICATORS
Indicator.
I Chemical Name.
pH
Colour Colour
in Acid in Alka-
Range. Solu- line So- "Kin'
tion. lution.
Colour Colour
Indicator. I Chemical Same. pH
Range.
in Acid in Alka-
Solu- line So- pKin
I tion. lution.
a-Naphthol- a-Naphtholphtha- 7'3- 87 Yellow Blue 84
phthalein lein
I Thymol blue
(base)
Thymol-sulphone- 80-- 96 Yellow Blue 89
; Phenol-
phthaJeill
Turmeric'
phthalein
Phenolphthalein
-
_-
83-100
80-100
Jlolm.u'- Reg.
.less--
Yellow Orange
96
-
Thymolphtha- Thymolphthalein 83-105 Colour- Blue 92
lein less
Alizarine p-Nitrobenzene- 101-120 Yellow Orange -
yellow R azo-salicylic red
acid
Brilliant cresyl (see above) 108-120 Blue Yellow -
blue (base) ...
Tropaeolin 0 p-Sulphobenzene- 11-1-127 Yellow Orange -
azo-resorcinol
Nitramine 2 : 4 : 6-Trinitro-
phenyl-methyl-
I 108-130 Colour-
less
Orange-
brown
-
nitroamine
I
dioxide under a pressure of one atmosphere has a pH of about 37 at
25 C. The analyst may therefore be dealing, according to the con-
ditions that prevail in the laboratory, with water having a pH between
the two extremes pH 37 and pH 7. Hence for indicators which show
their alkaline colours at pH values above 45, the effect of carbon
dioxide introduced during a titration, either from the atmosphere or
from the titrating solutions, must be seriously considered. This subject
is discussed again later (Section I, 32).
The colour-change intervals of most of the various indicators listed
in the table are represented graphically in Fig. I, 27, 2_ It will be
seen that the pH range between 0 and 13 is covered by the above
indicators.
The indicators at present most used in quantitative analysis are
methyl orange (as the simple or " screened" forms-see Section I, 29),
methyl red and phenolphthalein. The phthalein indicators merit much
more attention than has hitherto been given to them; this would be
the case if their many advantages, particularly their sharp colour
changes and slight sensitivity to carbon dioxide, were more widely
realised.
I, 28. Preparation of indicator solutions.-As a rule the stock solutions
of the indicators contain 05-1 g. of indicator per litre of solvent. If
the substance is soluble in water, e.g., if a sodium salt, water is the
solvent; in most other cases 70-90 per cent alcohol is employed. It
should now be stated that the new synthetic indicators, particularly the
sUlphonephthaleins and phthaleins which exhibit brilliant colour
changes, may be used with confidence in all those cases where the older
ones, largely natural products, were formerly employed.
Methyl orange. This indicator is encountered in commerce either as
the free acid or as the sodium salt.
54 Quantitative Inm'ganic Analysis
Dissolve 05 g. of the free acid in 1 litre of water, and filter the ~ld
solution if a precipitate separates.
Dissolve 05 g. of the sodium salt in 1 litre of water, add 152 ml. of
OIN-hydrochloric acid, and filter, if necessary, when cold.
Methyl red. Dissolve 1 g. of the free acid in 1 litre of hot water, or
dissolve in 600 ml. of alcohol and dilute with 400 ml. of water.
Phenolphthalein. Dissolve 5 g. of the reagent in 500 ml. of alcohol
and add 500 ml. of water with constant stirring. Filter, if a precipitate
forms.
Alternatively, dissolve 1 g. of the dry indicator in 60 m!. of ethylene.
glycol mono ethyl ether (cellosolve), b.p. 135 0 C., and dilute to 100 ml.
with distilled water: the loss by evaporation is less with this
preparation.
Thymolphthalein. Dissolve 04 g. of the reagent in 600 ml. of alcohol
and add 500 ml. of water with stirring_
IX-Naphtholphthalein. Dissolve 1 g. of the indicator in 500 ml. of
alcohol and dilute with 500 ml. of water.
Litmus. Commercial litmus contains, in addition to the colouring
matter (azolitmin), varying quantities of calcium carbonate, calcium
sulphate, etc. Purification is effected as follows. Digest 10 g. of the
commercial substance with 35 ml. of rectified spirit on the water-bath
for 1 hour and decant the alcohol; repeat this process twice so that
105 ml. of alcohol are employed in all. Extract the residue several
times with water (total volume 175 mI.-the first 25 mI. is discarded
as it contains most of the potassium carbonate), and allow to stand for
several days. Decant or siphon off the clear extract. This is of suit-
able concentration for most practical purposes.
As a general rule the use of litmus in quantitative neutralisations
should be avoided, for the solution may contain variable amounts of
the colouring matter. It is useful for qualitative tests, but then litmus
The Theoretical Ba8i8 of Quantitative AnalY8is 55
paper is to be preferred to the solution. Such indicators as bromo-
cresol purple or bromo-thymol blue, which cover approximately the
same pH range, are excellent substitutes for litmus; the colour changes
are very striking and'a pure product can be obtained, so that a uniform
solution is assured.
Azolitmin. This is the pure litmus colouring matter, and consists
largely of the blue potassium salt of (red) azolitmic acid. A solution
is prepared by dissolving 1 g. in I litre of water. It is not very much
Illore sensitive than good litmus solution.
Sulphonephthaleins. These indicators are usually supplied in the
acid form. They are renu.ered water-soluble by adding sufficient
sodium hydroxide to neutralise the potential sulphonic acid group.
One gram of the indicator is triturated in a clean glass mortar with the
appropriate quantity of O'IN -sodium hydroxide solution, and then
diluted with water to I litre. The following volumes of O'IN -sodium
hydroxide are required for I g. of the indicators: bromo-phenol blue,
150 ml.; bromo-cresol green, 144 m!.; bromo-cresol purple, 186 m!. ;
chloro-phenol red, 236 m!.; bromo-thymol blue, 16,0 ml.; phenol red,
284 m!.; thymol blue, 215 ml.; cresol red, 262 m!.; meta-cresol
purple, 262 ml.
Quinaldinic acid. Dissolve 1 g. in 100 ml. of rectified spirit.
Methyl yellow, neutral red, and congo red. Dissolve 1 g. of the indicator
in 1 litre of 80 per cent alcohol. Congo red may also be dissolved in
water.
p-Nitrophenol. Dissolve 2 g. of the solid in 1 litre of water.
Alizarine yellow R. Dissolve 05 g, of the indicator in 1 litre of recti-
fied spirit,
Tropaeolin 0 and Tropaeolin 00. Dissolve 1 g. of the solid in 1 litre of
water.
Many of the indicator solutions are available commercially already
prepared for use. These should be bought from the actual chemical
manufacturers, who will usually supply full details as to the method of
preparation, concentration of the solution, etc.
I, 29. Mixed indicators.-With some indicators, e.g., methyl orange,
the colour change is not easily detectable, particularly in artificial light.
A sharper and more pronounced colour change may often be obtained
by using a suitable mixture of the indicator and an indifferent dye.
Thus for methyl orange, Moerk (1921) used a mixture of 1 g. of methyl
orange and 25 g. of indigo carmine dissolved in 1 litre of water; the
colour change from the alkaline to the acid side is yellowish -green -+
grey -7>- violet, the grey stage being reached at pH 4. This indicator is
stored in a brown bottle. Hickman and Linstead (1922) obtained a
somewhat better effect by dissolving a mixture of 1 g. of methyl orange
and 14 g. of xylene cyanol FF* in 500 ml. of 50 per cent alcohol;
here the colour change from the alkaline to the acid side is green --+ grey
--+ magenta, the middle (grey) stage being obtained at pH 38. The
* The constitution is : /CH a
0 00 10 20
50 05 15 25
75 08 18 28
90 13 23 33
98 20 30 40
I 99 23 33 43
995 26 36 46
99'8 30 40 50
999 33 43 53
1000 70 70 70
1001 107 97 87
1002 HO 100 90
1005 114 104 94
101 11-7 107 97
102 120 110 10'0
110 127 117 107
125 132 122 112
150 135 12'5 115
200 140 130 120
i
14 14
~- l -
~
13
12
;( J.....--"o~ I3
12
~l--'_
, II 1../o 1
10
rl 1o
9 9
8 8
pH pH
7 7
6 6
5 6
4 4
3 / 3
J.--"- ~
O )J.-.-'
2 2
~~
)..--'"'
)
v
o f.-- J0i- 0
o 20 40 60 80 100 120 140 160 180 200
Alkali added, ""
FIG. 1, 32, I.-Neutralisation Curves of 100 m!. of Hel with NaOH of same
Normality (Calculated).
The Theoretical Basis of Quantitative Analysis 59
In quantitative analysis we are especially interested in the changes
of pH near the equivalence point. This part of Fig. 1, 32, 1 is accord-
ingly shown on a larger scale in Fig. 1, 32, 2, on which are also indicated
the colour-change intervals of some of the common indicators.
With N solutions, it is evident that any indicator with an effective
range between pH 3 and 105 may be used. The colour change will be
sharp and the titration error negligible.
With OIN solutions, the ideal pH range for an indicator is limited to
45-9,5. Methyl orange will exist chiefly in the alkaline form when
998 ml. of alkali have been added, and the titration error will be 02
per cent, which is negligibly small for most practical purposes; it is
14
:1 "". , , ,.,",
Thymol phthalein
/'
'// +-- ~
-n
V
lPhenol red
~ Bromo- thymol
blue
J Methyl red
V
4 Jl~ J ~
~ Methyl ~range
~~ V V)
3
~V
v
~
1 Indicator
RangeS'
0
98 99 100 101 102
Alkali added. ml.
FIG. I, 32, 2.-Neutralisation Curves of 100 ml. of HCI with NaOH of same
.....
Norm!',ljty in Vicinity of Equivalence Point (Calculated) .
'
jUl. oj OIN-NaOH
Used. OIN -Acetic Acid pH. I
OIN-HA (Ka = I X 10- 7 )
pH.
\
0 29 40
10 38 60
25 43 65
50 47 70
90 57 80
990 67 90
995 70 93
99'8 74 97
999 77 98
1000 87 99
~
,
14
13
12
jlV~ -
11
/_
'~I
Thymol phthalein
9
({~J , ,. ri'' '
.,--,V :,6~ I, " "' ,MM"'"
I,'B :;:Y"/
8
pH
7r--
6 <;$) ~
If !Methyl red
4
~,0 ~ ~
~MethYl orange
,"
~V
2 II
Indicator
Ranges
Vo 20 40 60 80 100 120 140 160 180 200
Alkali added. ml.
FIG. I, 33, I.-Neutralisation Curves of O'lN-Acetic Acid and of OlN-Acid
(K. = 1 X 10-7 ) with O'IN-Sodium Hydroxide (Calculated).
the titration curve that neither methyl orange nor methyl red can be
used as indicators. The equivalence point is at pH 8'7, and it is neces-
sary to use an indicator with a pH range on the slightly alkaline side,
such as phenolphthalein, thymolphthalein, or thymol blue (pH range,
as base, 8'0-9'6). For the acid with Ka = 10-7 , the equivalence point is
at pH = 10, but here the rate of change of pH in the neighbourhood
62... Quantitative Inorganic Analysis
of the stoichiometric point is very much less pronounced, owing to
considerable hydrolysis. Phenolphthalein will commence to change
colour after about 92 ml. of alkali have been added, and this change
will occur to the equivalence point; thus the end point will not be
sharp and the titration error will be appreciable. With thymol-
phthalein, however, the colour change covers the pH range 9'3-10'5;
this indicator may be used, the end point will be more sharp than for
phenolphthalein, but nevertheless somewhat gradual, and the titration
error will be about 02 per cent. Acids that have dissociation constants
less than 10-7 cannot be satisfactorily titrated in O'IN solution with a
simple indicator.
In general, it may be stated that weak acids (Ka > 5 X 10-6 ) should
be titrated with phenolphthalein, thymolphthalein, or thymol blue as
indicators.
I, 34. Neutralisation of a weak base with a strong acid.-We may
illustrate this case by the titration of 100 ml. of O'IN-ammonium
hydroxide (Kb = 18 X 10-5 ) with OIN-hydrochloric acid at the
ordinary laboratory temperature. The pH of the solution at the
equivalence point is gi~-en by the equation (Section I, 19) :
pH = iKw - ipKb - i log c
= 7 - 237 - t( - 1-30) = 5-28
For other concentrations, the pH may be calculated in the following
manner. Using the approximate mass action expression:
[NH4 +] X [OH-]f[NH 40H] = Kb . (1)
or (OH-l = [NH 40Hl X K b /[NH 4+] (2)
or pOH = log [Salt]j[Base] +
pKb _ (3)
or pH = pKw - lJKb - log (Salt]j[Base] (4)
999 63 40
100-0 5-3 4-0
I
14
13
12
'~ '/'\1
''"''"""~'"
10 ~IT)",
1\ oniu It PHENOL
"'0'"
AL0.,
PHTHALEIN
8 ~
. ~ pH
':; ~: . ~8a~e. I( /
7 f-.::.:.0 '>
't',.
~~"n_
6
5
\
4
METHYL OIIANGE
3
1 ~
r-.
I
~ Indicator Ranges
0
o 20 >\0 60 80 100 120 1>\0 160 180 100
ACID ADDED. ML.
FIG. I, 34, I.-Neutralisation Curves of 100 m!. OIN-Ammonium Hydroxide (Kb =
18 X 1()-5) and of O'IN-Base (Kb = 1 X 10- ) with O'IN-Hydrochloric Acid.
'
[H+] = JK;K;C
Kl +c
Provided that the first stage of the acid is weak and that Kl can be
neglected by comparison with c, the concentration of salt present, this
expression reduces to [H+] = -yiK 1 K 2 , or pH = tPKl ipK 2. +
With a knowledge of the pH at the stoichiometric point and also of
the course of the neutralieation curve, it should be an easy matter to
select the appropriate indicator for the titration of any dibasic acid
for which KIIK2 is at least 10"'. For many dibasic acids, however, the
two dissociation constants are too close together and it is not possible to
differentiate between the two stages. If Kzis not less than about 10-7 , all
* For details, see, for example, S. Glasstone, The Electrochemistry of Solutions. Third
Edition, pp. 224 et seq. (Methuen, 1945.)
t See, for example, ibid., pp. 232 et seq.
The Theoretical Basis of Quantitative Analysis 65
the replaceable hy~rogen n;ay ~e titrate~, e.g., s~l;phuric acid (primary
stage-a strong aCId), oxalIc aCId, malomc, SUCClillC, and tartaric acids
(for dissociation constants, see Table II, Section I. 4).
Similar remarks apply to tribasic acids. These may be illustrated
by reference to orthophosphoric acid, for )Yhich KI = 75 X 10-3 ,
K2 = 62 X 10-8 , and K3 = 5 X 10-13 , Here Kl/K2 = 12 X 10 5 and
Kz/K3 = 12 X 105 , so that the acid will behave as a mixture of three
monobasic acids with the dissociation constants given above. Neu-
tralisation proceeds almost completely to the end of the primary stage
before the secondary stage is appreciably affected, and the secondary
stage proceeds almost to completion before the tertiary stage is appar-
ent. The pH at the first equivalence point is given approximately
14
J
L.).... l-
12
V
1
II
'''''~~''''
0
\-l PHENOL
PHTHALEIN
8
:J
pH
1/
V
Ii
I"'~'
[/11
V 1"''"
METHYL ORANGE
I..-'v !d'
1 21 "-
:r: d' Indicator Ranges
o ~l ';1
',"M
::.:
o 1020 )040 50 60 70 80 901001101201)0140150
ALKALI ADDED, ML.
13
'.
12
Ii'--.
j'-...i"----..
10
i!1;:::~~
'-....
9 i'-..
~
8 ~ Thymol blue
pH
7
6
'" -- -
'-.... i'...
.
5 ~
\~ 0l blue
4
-7
~~:'IethYI
~ orange
3
2
Indicator
Ranges
o Z
o m w w ~ W 00 ro 00 00 ~
or pAg+ +
pCI- = 992 = pAgCI
8
~ ~cg_Cl- " pSAgI
6
i\ .,
6 pSAgCl
4 I
3
.\.. ~Agt-
)
A.gCl+~
2
[A g +] -- SAgO! -
[Cl-] -
J SA~,CrO.
[Cr0 4--]
SAgO! 12 X 10-10
----r'========~ = 92 X 10-~
YSAg ,JrO.
2
y'17 X 10-12
At the equivalence point [Cl-] = y'SAgOI = 11 X 10-5 If silver
chromate is to precipitate at this chloride-ion concentration:
[Cl-] )2 = (1.1 X 10- 5)2
[Cr0 4--] = ( 9.2 X 10-5 9.2 X 10-5 = 14 X 10-2
[Ag+] = J SAg,CrO.
01'0 4
= Jl.7
3 X
X 10-
10-3
12
= 24
X
10-5
[A g +] = Jl'7 12
X 10- = 11
1.4 X 10-2 X
10-5
.
Ag+ +
CNS - ? AgCNS
'
The two sparingly soluble salts will be in equilibrium with the solution,
hence:
_[Cl-] _ SAgOI _ 1;2 X 10-10 = 170 .".
[CNS-] - SAgC'NS - 71 X 10-13
When the excess of silver has reaoted, the thiocyanate may react
'With th~ 'Dih~'\: ~hkid~, 'Din.~~ 'Dil,,~'\: thioo'Ye.l\e.+..R, i'D th~ l~'D'D-ool\\bl~ 'De.lt
until the ratio [Cl-]j[CNS -] in the solution is 170 :
AgCl + CNS - ~ AgCNS + Cl-
This will take place before reaction occurs with the ferric ions in the
solution, and there will consequently be a considerable titration error.
It is therefore absolutely necessary to prevent the reaction between
the thiocyanate and the silver chloride. This may be effected in
several ways, of which the first is probably the most reliable: (i) the
silver chloride is filtered off, and the filtrate and washings are titrated;
(ii) the silver chloride is coagulated, and thus rendered less reactive by
boiling, and the mixture is cooled and titrated; (iii) the addition of a
few ml. of ether or, preferably, of I :rnl. of nitrobenzene, which causes
coagulation, before back titration.
With bromides, we have the equilibrium:
_[Br-] _ SAgEr _ 35 X 10-13 = 0.5
[CNS-] - SAgCNS - 71 X 10-13
The titration error is small, and no difficulties arise in the determination
of the end point. Silver iodide (S.P. 17 X 10-16 ) is less soluble than
the bromide; the titration error is negligible, but the ferric-iron
indicator should not be added until e:l{cess of silver is present, since the
dissolved iodide reacts with the ferric iron:
2Fe+++ + 21- ~ 2Fe++ + 12
C. Use of adsorption indicators. K. Fajans (1923-24) has introduced
a new type of indicator for precipitation reactions as a result of his
studies on the nature of adsorption. The action of these indicators is
due to the fact that at the equivalence point the indicator is adsorbed
by the precipitate, and during the process of adsorption a change
* According to Bent and French (1941) the coloration is due to the FeCNS++ ion:
Fe+++ +
CNS - ~ FeCNS++
The Tlteoretical Basis of Quantitative Analysis 75
occurs in the indicator which leads to a substance of different colour;
they have therefore been termed adsorption indicators. The substances
employed are either acid dyes, such as those of the fluorescein series,
e.g., fluorescein and eosin which are utilised as the sodium salts, or
basic dyes, such as those of the rhodamine series (e.g., rhodamine 6G),
which are applied as the halogen salts.
The theory of the action of these indicators is based upon the pro-
perties of colloids (see Section I, 56). When silver nitrate solution is
titrated with a solution of a chloride, the precipitated silver chloride
adsorbs chloride ions (a precipitate has a tendency to adsorb its own
ions); this may be termed the primarily adsorbed layer, and it will
hold by secondary adsorption oppositely charged ions present in solution
(shown diagrammatically in Fig. I. 41, 1, a). As soon as the stoichio-
metric point is reached, silver ions are present in excess; these will now
be primarily adsorbed, and nitrate ions will be held by secondary
adsorption (Fig. I, 41, 1, b). If fluorescein is also present in the
solution, the negative fluorescein ion, which is much more strongly
adsorbed than the nitrate ion, is immediately adsorbed, and will reveal
.,,
I
NO; ~Ag
,,
+
,,
,'8\
, Ag+
Agel
-",
Ag+;NOj
,
,
,,
.
,,
'
(a) ( b)
FIG. 1,41, l.-(a) AgCl precipitated in the presence of excess of Cl-.
(b) AgCl precipitated in the presence of excess of Ag+.
its presence in the precipitate, not by its own colour, which is that of
the solution, but by the formation of the red (or pink) silver fluorescein-
ate on the surface with first trace of excess of silver ions. An
alternative view is that during the adsorption of the fluorescein ion
a re-arrangement of the structure of the ion occurs with the formation
of a coloured substance. It is important to notice that the colour
change takes place at the surface of the precipitate. If chloride is now
added, the suspension will remain pink until chloride ions are present
in excess, the adsorbed silver will then be converted into silver chloride,
which will then primarily adsorb chloride ions. The fluorescein ions
secondarily adsorbed will pass back into solution, to which they impart
a greenish-yellow colour.
The following conditions will govern the choice of a suitable indi-
cator:
(i) The precipitate should separate as far as possible in the
colloidal condition. Large quantities of neutral salts, particularly
of polyvalent ions, should be avoided owing to their coagulating
effect. The solution-should not be too dilute, as the amount of
precipitate formed will be small and the colour change far from
sharp with certain indicators.
(ii) The indicator ion must be of opposite charge to the ion of
the precipitating agent.
76 Quantitative Inorganic Analysis
(iii) The indicator ion should not be adsorbed before the par-
ticular compound has been completely precipitated, but it should
be strongly adsorbed immediately after the equivalence point.
The indicator ion should not be too strongly adsorbed by the
precipitate; if this occurs, the adsorption of the indicator ion
may be a primary process and will take place before the equivalence
point, e.g., eosin (tetrabromofluorescein) in the chloride-silver
titration.
EO
Electrode. Electrode Reaction.
. (volts).
Red
'------y---J
Ox
The electrode potential which is established when an inert or unattack-
able electrode is immersed in a solution containing both oxidant and
reductant is given by the expression:
E T-- EO + -F
RT I oge~
ao x (1)
n aRed
E = EO + 0.0591
5 1og [Mn0 [Mnl-I]
X [H+]8*
4-] ( t 25 0 )
a .
The concentration (or activity) of the water is taken as constant, since
it is assumed that the reaction takes place in dilute solution, and the
concentration of the water does not change appreciably as the result of
the reaction. The equation may be written in the form:
E = EO + 0.0591
5 1og [Mn0
[MnH]
+ 0'0591
4-]
5 1og [H+]8
This enables us to calculate the effect of change in the ratio [Mn0 4-]/
[Mn++] at constant hydrogen-ion concentration, other factors being
maintained constant. In this particular case difficulties are experienced
in the latter calculation owing to the fact that the reduction products
of the permanganate ion vary at different hydrogen-ion concentrations.
In other cases no such difficulties arise, and the calculation may be
employed with confidence. Thus in the reaction:
H3As04 + 2H+ + 2 ~ H3As03 + H 2 0
E -- EO + 0.0591
2 1og
[H 3As0 4]
[H3
X [H+]2 ( t 25 0 )
As0 3] a .
or E - EO
-
+ 0'0591
2 1og [H
[H3
3As0 4] + 0'0591 1 [H+]2
3] 2 og
As0
We are now in a position to calculate the equilibrium constants of
oxidation-reduction reactions, and thus to determine whether such
reactions can find application in quantitative analysis. Let us con-
sider first the simple reaction:
01 2 + 2Fe++ ~ 201- + 2Fe+++
The equilibrium constant is given by :
[01-]2 X [Fe+++]2
[01 2] X [Fe++]2 = K
The reaction may be regarded as taking place in a voltaic cell, the two
half-cells being a 01 2,201- electrode and a Fe++,Fe+++ electrode. The
reaction is allowed to proceed to equilibrium; the total voltage or
e.mJ. ofthe cell will then be zero, i.e., the potentials of the two electrodes
will be equal :
0059 [01 2] _ 0059 [Fe+++]
E Cl,,2Cl- +
-2- log [01-]2 - E Fe++,Fe+++ +
-I-log [Fe++]
Now E0 01 ,,2Cl- = 136 volts and EOFe++,Fe+++ = 075 volts, hence
[Fe+++]2 X [01-]2 061
log [Fe+ ]2 X [01 2] = 0.02965 = 2067 = log K
T
or K = 47 X 1020
* More accurately, activities should be employed. The square brackets denote
molecular concentrations.
The Theoretical Basis of Quantitative Analysis 85
The large value of the equilibrium constant signifies that the reaction
will proceed from left to right almost to completion, i.e., a ferrous salt
is almost completely oxidised 9Y chlorine.
Consider now the more complex reaction:
Mn0 4 - + 5Fe + 8H+ ~ Mn++ + 5Fe+++ + 4H 0
H
2
E
= EO + 0.059 1 [Mn0 4-] X [H+]8
5 og [Mn++]
= 1.52 + 0059 l' [MnO 4-] X [H+]8
5 og [Mn++]
The partial equation (2) may be multiplied by 5 in order to balance
( 1) electrically:
5Fe++ ~ 5Fe+++ 5" + (2')
For (2') as an oxidation-reduction electrode:
o 0059 [Fe+++]5
E = E +
-5- log [Fe"p
0059 [Fe+++]5
= 077 + 5 - log [Fe++J5
Combining the two electrodes into a cell, the e.m.f. will be zero when
equilibrium is attained, i.e.,
1.52 + 0.059 l [Mn0 4 -] X [H+]8 = 0.77 + 0.059 l [Fe+++]~
5 og [MnH] 5 og [Fe++]5
are known; from the value of K thus obtained, the feasibility of the
reaction in analysis may be ascertained:
I, 49. Change of the electrode potential during the titration of an
oxidant and a reductant. Oxidation-reduction curve.-In Sections I,
33-36 we calculated the change in pH during the titration of an acid
and a base, and we utilised the neutralisation curve thus obtained in
order (a) to specify the most suitable indicator for use in the process,
and (b) to compute the titration error in the quantitative neutralisation.
We shall now attempt to carry out parallel calculations for oxidation-
reduction processes. Let us study first a simple case which involves
only the valency change of ions, and is theoretically independent of the
hydrogen-ion concentration. A suitable example, for purposes of
, illustration, is the titration of 100 ml. of OIN-ferrous iron with OIN-
eerie cerium :
Ce++++ Fe++ ~ Ce+++ +Fe+++ +
The quantity corresponding to pH is the ratio [Ox]j[Red]. We are
concerned here with two systems, the ferrous-ferric ion electrode (I),
and the cerous-ceric ion electrode (2).
For (1) at 25 0 C. :
o 00591 [Fe+++] [Fe+++]
El = E} + -]- log lFe++] = + 075 + 00591 log [Fe++]
For (2), at 25 0 C. :
00591 [Ce++++] [Ce++++]
+ -I-log + 145 + 00591 log
.0
E2 = E2 [Ce+T+] = [Ce;-++]
15 0
ExcesS Ce +H+
1'40
:;:;.-r-
13
If
12 0
10 ,P.
0
,
09 0
08 I ~+ J
07 0
E ~ I
[Fe++] =
1 = 10-10
or pFe++ = 10
Thus pFe++ changes from 43 to 10 between 01 per cent before and
01 per cent after the stoichiometric
17
+1++/ Ce +~H
point. These quantities are of im- 0
portance in connexion with the use 16 Ce
-
of indicators for the detection of the
equivalence point.
It is evident that the abrupt
1'5
13
/ ----
t<\n~+/~
I
2Cr+++ Cr207
V
change of the potential in the neigh-
bourhood of the equivalence point
12 f-- C- I
<~-NH~<~ +
(I)
<:>-NH-<=>
I 0
{-
<=>-NH-~>-<=>-NH-(_>
(II) t
<
-~ -/=~-/=~- <~
_/-N-~=/--~=/-N- _/ + 2H+ + 2E
(III)
'The oxidation potential (EO rn ) is slightly higher (0'83 volt), and the
oxidised form has a reddish-violet colour resembling that of potassium
permanganate, but the colour slowly disappears on standing; phos-
phoric acid must still be present in order to lower the oxidation potential
of the system. The addition of phosphoric acid may be avoided by the
use of ortho-phenanthroline ferrous ion, N-phenylanthranilic acid, or
xylene cyanol FF as indicators.
A list of selected oxidation-reduction indicators, together with their
colour changes and oxidation potentials in acid medium, is given in
Table XVII.
92 Quantitative Inorganic Analysis
TABLE XVII.-SoME OXIDATION-REDUCTION INDICATORS
Colour Change.
Indicator. EO (at pH ='0).
OxidisEd Form. REduced Form.
. -
96 Quantitative Inorganic Analysis
0' 1, 8521; Co, 5, 3502, 3530; Cu, 2, 3247; Fe, 10, 3735; Li, 00
6708; Mg, 10, 2852; Mn,. 1, 4031, 4035; Ni, 15, 3525 ; K , 0'05, 7655
and Na, 0'01, 5890, 5896.
The :la,me photometer has been . suggested for the simultaneo
determination of all the alkali metals in mixtures, the determination
most of the rare earths in mixtures, the determination of tracea
strontium and calcium in barium, of silver in gold, of copper in mercury.
of cobalt in nickel, and also for the analysis of many alloys containin
iron, cobalt, nickel, copper, manganese, and chromium.
Emission spectrography. The emission spectra of elements may be
COLLIMATING LENS
FlO. I, 52, 1.
FIG. I, 52, 2.
Element
I Precipitated as
\
Weighed as
Pb 1. PbS0 4 ; 2. PbCr0 4 ; 1. PbS0 4 ; 2. PbCr0 4 ;
3. PbMo0 4; 4. Pb salicyl- 3. PbMo0 4 ; 4. Pb(C 7H s02N);
aldoximate ; 5. Pb(IOah; 5. Pb(IOah; 6. Pb0 2 *
6. Pb0 2.
ox.yquin~ldinNate
anthranilate; 6. Zn 8-hydr- 4. [Zn(C sH sN)2](CNS)2 ;
I (" 2-methyl- I 5. Zn(C 7 H 60 2N)z;
ox mate ); ,. Zn. 6. Zn(C lo H sON)2 ;
7. Zn.*
Mn 1. Mn(NH.)PO.,HzO. 1. Mn 2P Z07 or as
Mn(NH.)P0 4 ,Hp.
I
~~
1. (NH4 )zU Z07; 2. Uranyl 1. UaO g ;
" oxinate " ; 3. U (ous) cup- 2. U0 2(C 9 H 6 ONbC 9 HO,N;
ferron complex. 3. UaOs.
h 1. Th(C zO.)2; 2. Th sebacate; 1. ThO z ; 2. ThO z ; 3. ThO z'
3. Th(IO a).
W 1. Benzidine tungstate; 1. WO a ; 2. WO a ;
2. Tannin-antipyrine-tungstate 3. W0 2(C 9 H sON)2;
complex; 3. Tungstyl " oxin- 4. BaW0 4.
ate"; 4. BaW0 4..
Anions
S04--'
S--,
S03--'
S20a--
1. BaS0 4
I'
I
BaS0 4
104 Quantitative Inorganic Analysis
TABLE XVIII-Continued
Salt.
Coag_ Value. Salt. Coag. Value.
AICI a 0062 K.Fe(CN)6 0067
A1 2(SO.)a 0074 Ka Fe (CN)6 00!J6
FeCls 0136 K 2SO. 022
CaC1 2 0649 K 2Cr 20 7 019
BaCI 2 0691 K 2CrO. 033
MgC1 2 0717 K 2C2O. 024
Ba(NO;)2 0687 KBr0 3 31
KCI 495 KC:~B 47
NaCl 510 KCl 103
LiCI 584 KN0 3 131
KN0 3 500 KBr 138
HCI 308 KI 154
Concentration I
of Reagents.
(Q - S)/S. I Type of Precipitate.
(I) 6 ~H (II)
,f'",/~/OH
I II I
~/"'~ (IX)
Cu++ + 2NH CH2CH 2NH2= [Cu(NH 2CH2CH 2NH 2)2J++ == [Cu en ]++
2 2
This reacts with the complex ions [HgI4J- - or [CdI 4]- - to yield the
insoluble complex salts [Cu en 2] [HgI 4] and [Cu en 2] [CdI 4] respectively:
The complex salts are insoluble in water, 95 per cent alcohol, and ether,
and hence may be employed in the rapid determination of mercury,
cadmium, and copper respectively (G. Spacu and co-workers, 1929-+-).
The mercury complex is stable in air and in a vacuum, and its precipita-
tion is unaffected by the presence of ammonium salts; a valuable rapid
method is thus available for the determination of mercury. The
cadmium complex has similar properties, but is slightly soluble in the
presence of ammonium salts or in. strongly ammoniacal solution; the
experimental details for the determination of cadmium are similar to
those given for mercury (Section IV. 160) except that precipitation is
effected in neutral solution with reagent (a) (see below).
126 Quantitative Inorganic Analysis
The process also permits of a quantitative separation of copper and
mercury. The acid solution of both metals is treated with ammonia
solution until nearly neutral and is then rendered alkaline with ethyl-
enediamine. The solution is heated to boiling, treated with excess of
potassium iodide and copper ethylenediamine nitrate solution and
allowed to cool; the mercury complex is filtered off and weighed (Section
IV, 160). The copper is determined in another portion of the solution
as in Section IV, 19F.
The reagent may be prepared by either of the following methods:
(a) Heat an aqueous solution containing 1 part of cupric nitrate and
2 parts of ethylenediamine on a water-bath until a crust forms on the
surface of the violet-blue solution. Allow to cool, filter off the separated
crystals of [Cu en 2[(N0 3 )z,2H 20 at the pump, and wash them several
times with alcohol, followed by ether. A concentrated solution of this
salt is used for precipitations.
(b) Treat a solution of cupric sulphate with an aqueous solution of
ethylenediamine (five to six times the theoretical quantity) until the
dark blue-violet coloration, due to the [Cu en 2]++ ion, appears and does
not increase in intensity upon further addition of ethylenediamine.
The presence of excess of the latter in the reagent has no harmful
influence. Here the reagent consists of a solution of [Cu en2.1S0 4' and is
as satisfactory as (a) for determinations of mercury.
P. 8-Hydroxyquinaldine (XV). The reactions of 8-hydroxyquinaldine
are, in general, similar to 8-hydroxyquinoline (e), but unlike the latter
it does not produce an insoluble complex with aluminium. In acetic
acid-acetate solution precipitates are formed with bismuth, cadmium,
copper, ferrous and ferric iron, chromium, manganese, nickel, silver,
zinc, titanium (TiO++), molybdate, tungstate, and vanadate. The
same ions are precipitated in ammoniacal solution with the exception
of molybdate, tungstate, and vanadate, but with the addition of lead,
calcium, strontium, and magnesium; aluminium is not precipitated, but
tartrate must be added to prevent the separation of
aluminium hydroxide.
8-Hydroxyquinaldine (2-methyl-oxine) is a pale
yellow, crystalline solid, m. p. 72 C.; it is insoluble
(XV) in water, but readily soluble in hot alcohol, benzene,
and ether. The reagent is prepared by dissolving 5 g ..
of 8-hydroxyquinaldine in 12 g. of glacial acetic acid and diluting to
100 ml. with water: the solution is stable for about a week.
ELECTRO-ANALYTICAL METHODS
..fI!.
,......... r- Cu
"2
/' V
v
1'0 .L J....-- I- r- Ag
.L.
f/
~
o
> os LV Au
.., 1//
W
1--'- '--
I-:' ~ t---
~
00' 6
~
w
>
o
1lL
I
'{ V
~
v- - l- l -I-"
l't $1'11
/
o 2j_
II Pt black-t--
o~
o os 1'0 ,s
CURRENT DENSITY. AMPS. PER SQ. CM.
FIG. I, 67, 1.
Since Eca/. sat. is known, the electrode potential of the cathode can
be easily referred to the hydrogen scale. In order to prevent the
cathode potential from exceeding a fixed value, it is simply necessary
to decrease the potential applied to the cathode and anode by increasing
the value of the resistance R. Thus in Fig. I, 71, 2, are plotted the
cathode-calomel potential E and the electrolysing current C against
time for the deposition of copper from a solution containing about 04 g.
of copper, about 02 g. of tin, and 15 per cent sulphuric acid. The
cathode potential became more negative rapidly at the commencement
of the electrolysis as the platinum-gauze electrode was covered with
copper and as the copper was deposited. When the potential _had
fallen to - 035 volt towards the saturated calomel electrode the applied
voltage had decreased, causing a decrease in the current. The applied
potential (to the anode and cathode) was reduced by increasing the
resistance R so that at no time was the cathode more than O 35 volt
negative to the calomel electrode. Ultimately all the copper separates,
but the current never falls to zero owing to the minor cyclic side re-
actions of the stannous and stannic ions. It must be emphasised that
rapid stirring or rotation of the anode is essential; concentration
polarisation effects are thereby reduced and higher current densities
(with consequent decrease in the time required for the electro-analysis)
may be employed.
138 Quantitative Inorganic Analysis
It may be noted that in evaluating the limiting cathode potential
to effect the separation of one metal from another, a simple com-
putation of the equilibrium potential from the Nernst equation
(compare Sections I, 66 and I, 68) is not sufficient. The equilibrium
potential must be increased by the overvoltage (or polarisation
potential). The latter depends upon the rate of stirring and on
the current density as well as upon the nature of the metal surface;
in consequence, the limiting potential must be established more or
less empirically.
Anodic re-oxidation of the metal if it can exist in more than one
valency state or any reaction between the plated metal and the anodic
oxidation products must be reduced to a minimum for trustworthy
results, and also to minimise the time required for the deposition. This
may be achieved by such methods as (i) the use of a reducing agent
25 +0'1
V>
f--
...J
o
" 2'0 2:-
;(
V>
w
~
'"
b
~ "5 -0"
~ "-
...Z .J
l:
~I'O c -02 g
::J u
u I
'"
o
0'5 -03~
f--
u
0 '-~~---:'-10--..J.15---:'20:----:'25-0'4
0
TIME (MINUTES)
FIG. I, 71,2.
AI, Bi, Be, Ca, Cd, Cr, Co, Fell, Pb, Mn, Ni, Os, Pd, rare earths, Rh, Ag,
Th, Ti, W, U, and Zr are not extracted_
Xn = Xo
KTV
( KW + L
)n
where K is the distribution coefficient between water and the given solvent
(compare Section I, 60). It follows, therefore, that the best method
of extraction with a given volume of extracting liquid is to employ
several fractions of the liquid rather than to utilise the whole quantity
in a single extraction.
Let us take a particular example. Let us suppose that we
shake 50 mI. of water containing 01 g. of 'iodine with 25 mL
of carbon tetrachloride. The distribution coefficient of iodine
between water and carbon tetrachloride at the ordinary laboratory
temperature is I/S5, i.e., at equilibrium the iodine concentration in the
aqueous layer is 1/S5th of that in the carbon tetrachloride layer. We
will compute the weight of iodine remaining in the aqueous layer after
one extraction with 25 mL and also after, say, three extractions with
833 ml. of the solvent by application of the above formula. The forrper
can be simply computed as follows. If Xl g. of iodine remains in
the 50 ml. of water, its concentration is xd50 g. per ml.; the concentra-
tion in the carbon tetrachloride layer will be (0'1 - Xl) 125 g. per mL
Hence:
142 Quantitative Inorganic Analysis
The concentration in the aqueous layer after three extractions with
833 ml. of carbon tetrachloride is given by :
,
)3
.
(1/85) X 50
X3 = 01 ( (50/85) + 8.33 = 0'0000145 g.
The extraction may therefore be regarded as vi~ually complete.
If the distribution coefficient is favourable, a separating-funnel may
be employed; if it is comparatively small, some continuous form of
extraction apparatus is to be preferred. *
= 0.6745 Jd t
2
+ d 2 + ....... d,,2
2
n-l
The Theoretical Basis of Quanl'itative Analysis 145
where d 1 , d 2 , etc., refer to the deviations froIn the mean, and n is the
number of determinations. The probable error of the arithmetical
mean of a whole series of determinations is given by :
Probable error of the arithmetical mean
n(n - 1)
Probable error of a single determination
~---.---
v'n
In both calculations .~ is usually substituted for 06745.
The problem sometimes arises of evaluating a series of results
obtained by two or more analysts who have followed the same method
to the best of their ability, or even different methods, provided all
obvious errors inherent in the method have been eliminated. It is
desirable for this purpose to employ a more reasonable or conservative
estimate of the uncertainty in each analyst's results than that furnished
by th~ l}l"obab\~ ~1'1'o1' 01' d~viation. If the individ\lal1'~'i!,\llt"" a1'~ avail-
able, the probable error of each analyst's mMn results should be com-
puted and then some reasonable multiple of it taken as an expression
of the uncertainty in the result. No fixed multiple of the probable
error is universally employed, but 3 and 5 are frequently used. For
. purpose of illustration we shall employ the factor 3 to denote the
reasonable uncertainty in the arithmetical mean. This is then added
to, or subtracted from, the arithmetical mean to obtain the reasonable
limits represented by the result. Sets of results so treated are regarded
as consistent if they show at least one common value within their reason-
able limits. An example will make this clear. The table below con-
tains the results obtained by two analysts for the percentage of a
constituent A in a certain ore: the various quantities referred to in the
preceding discussion have also been calculated.
Probable Probable
Error of Reason
Error of able
Aritfa- Mean a Single the
Percentage oj Limit oj
Analyst. metical Devia- Arith
A Found. Deter the
Mean. tion. mina metical llfean.
tion. Mean.
6825 - - - - -
1 6827 6830 004 0032 0016 ' 0048
6833 - - - - -
6835 - - - - -
6820 6826 - - - - -
6821 6826 - - - - -
2 6821 6827 6824 0027 002 0007 002
6822 6828 - - - - -
6825 - - - - -
FIG. II, 2, 1.
,
the central beam support. The two terminal agate or pure corundum
knife edges, fixed at equal distances from the central knife edge, each
support a suspension (stirrup) from which the pans are hung, contact
being made upon agate or pure corundum planes fixed to the stirrups.
A long pointer is attached to the centre of the beam: this moves over
a scale at the foot of the pillar and serves to indicate the deflection of the
beam from the horizontal position when the balance is in operation.
The balance is levelled with the aid of levelling-screws and a plumb line
suspended from the column; in some balances a pair of spirit levels
are provided. In the figure the whole of the beam is divided into 100
equal parts so that weight adjustments smaller than 10 mg. can be
made readily by moving a small piece of platinum or gold wire (the
rider) along the beam by means of the rider hook and rider carriage.
For the beam graduated as shown in the figure a 5-mg. rider is employed;
in many balances only the right half of the beam is graduated, a 10-
152 Quantitative Inorganic An~ly8i8
m$" rider is then necessary. A small weight is attached to the pointer;
thIS serves to move the centre of gravity and thereby alter the sensitivity
of the balance. The adjusting screws at the ends of the beam are
employed for the purpose of adjusting the equilibrium position of the
pointer so that it rests at the centre of the scale, thereby ensuring that
the beam is horizontal when unloaded. In the better type of balances,
the sensitivity and equilibrium position of the pointer are adjusted
by means of a screw-nut device attached to
the centre of the beam behind the rider bar
and is shown diagrammatically in Fig. II, 2,
2; the screws at the end of the beam and on
the pointer are then, of course, omitted.
In order to protect the knife edges from
undue wear and from injury during the
FIG. II, 2, 2. transfer of weights and objects, the balance
is provided with a device whereby the moving
parts can be raised so that the knife edges and planes are very slightly
separated. This is operated by means of a large screw attached to the
base of the balance, placed either centrally in the front of the base as
shown in the figure, or, in some cases, in the centre of the left-hand
side of the base. In many balances the beam arrest is combined with
the pan arrest; in others, the pan-arrest mechanism is separately con-
trolled by a push button (not shown in the figure).
II, 3. The requirements of a good balance.-These are:
(a) The balance must be accurate and give the same result in successive
weighings.
This requisite is obtained if the arms are of equal length, if the beam
is rigid and does not bend appreciably under load, and if all the three
knife edges lie in the same plane and are parallel to one another.
(b) The balance must be stable, that is, the beam must return to the
horizontal position after swinging.
This is attained by a proper adjustment of the centre of gravitY.
(c) The balance must be sensitive, that is, 01 mg. should be readily
detectable with average loads.
We may define the sensitivity of a balance as the l\>ngular deflection rJ.
of the beam when a known small weight is added. It can be shown
that the angle ~ is determined by the excess of weight w producing the
deflection ~, the length of the balance arm d, the weight of the be~m
W, and the distance between the centre of gravity and the point ~f
support of the beam h. Expressed mathematically :*
wd
tan ~ = Wi!,
Since ~ is small, we may put tan ~ =~. The angular deflection of the j
beam is equal to the angular deflection of the pointer, and the latter is i
directly proportional to the number of divisions between the two points
of rest on the scale at the foot of the beam. This leads directly to the
usual definition of sensitivity, viz., the sensitivity t of a balance is the
number of scale divisions that the rest point (or equilibrium point) is
displaced by an excess of weight of 1 mg.
* For deduction, see H. A. Fales and F. Kenny, Inorganic Quantitative Analysis,
1939, p. 90 (AppletonCentury).
t Also termed sensibility and sensitiveness.
Technique of Quantitative Analysis 153
It follows from the above expression that: (i) the longer the balance
arms, the greater is the sensitivity; (ii) the lighter the beam, the greater
is the sensitivity; and (iii) the smaller the distance between the point
of suspension of the beam and the centre of gravity, the greater is the
sensitivity. These conditions for maximum sensitivity are unfortun-
ately conflicting with one another. Thus long arms are incompatible
with minimum w~ight. The length of the arm is also limited by the
fact that the time of swing of the pointer, which must not be excessive,
increases with its length. It is also important that the balance beam
be rigid in order that the centre of gravity, and therefore the sensitivity,
should not change appreciably with the load. The ceptre of gravity
must always be below the central knife edge, otherwise the balance
will be in neutral or unstable equilibrium. The sensitiveness may be
changed by moving the small weight attached to the pointer or, in
some balances, by rotation of the nut on the screw attached to the
central portion of the beam, which affect the position of the centre of
gravity. In general, a balance adjusted to give a deflection of three
to four scale divisions per milligram is quite satisfactory for macro-
quantitative work.
(d) The period of oscillation should be short.
This is necessary in order that weighings can be made rapidly. For
this reason "short-arm" balances, which have a period of swing of ...
5-10 seconds, are almost universally employed in analytical practice.
The so-called "long-arm" balances, although more sensitive, have a
long time of swing (about 15 seconds) which renders weighing a tedious
process.
Sensitivity and maximum load of a balance. In an ideal balance, free
from friction and with a perfectly rigid beam, the sensitivity would be
independent of the load. Most balances, however, exhibit a decreasing
sensitivity with increasing load, and this change of sensitivity
provides a good criterion as to the maximum safe load that a balance
can carry. The criterion is: no greater load should ever be placed
upon the balance pans than the load at which the sensitivity becomes
40 per cent of its maximum value (see Section II, 6 (a) and Fig.
II, 6, 1).
11,4. Weights, reference masses.-The determination of the mass of an
object with an equal-arm balance necessitates the use of a series of
reference masses termed weights. For scientific work, the international
metric system of weights and measures is employed. The fundamental
standard of mass is the international prototype kilogram, which is a
mass of platinum-iridium alloy made in 1887 and deposited in the
International Bureau of Weights and Measures near Paris. It repre-
sents as closely as possible the mass of 1000 g. of water at the tempera-
0
ture of its maximum density (4 C.). 'Authentic copies of the standard
are kept by the appropriate responsible authorities * in the various
countries of the world; these copies are employed for the comparison
of secondary standards, which are used in the calibration of weights
for scientific work. The unit of mass that is almost universally
employed in laboratory work, however, is the gram, which may be
defined as the one-thousandth part of the mass of the international
prototype kilogram.
* The National Physical Laboratory (N.P.L.) in Great Britain, the Bureau of
Standards in U.S.A., etc.
154 Quantitative Inorganic Analysis
Multiples and sub-multiples of units in the metric system are indi-
cated by the following prefixes: . \
kilo = a thousand times; milli = a thousandth part, or 000~;
hecto = a hundred times; centi = a hundredth part, or 0'01;
deca = ten times; deci = a tenth part, ?r 01.
The following weights are frequently encountered: kilogram (kg.),
decigram (dg.), centigram (cg.), and milligram (mg.).
An ordinary set of analytical weights contains the following: grams:
100, 50, 20, 10, 10, 5, 2, 1, 1, 1 (or 5, 2, 2, 1); milligrams: 500, ,200,
100, 100, 50, 20, 10, 10, 5, 2, 2, 1. Weights smaller than 10 mg. are
not actually used in weighing, and are therefore not really essential.
In addition to the weights, a set includes two" riders," which are small
weights of 5 or 10 mg. denomination, made of platinum, gold, or alumin-
ium wire, for use on the beam of the balance. The weights from 1 g.
upwards are generally constructed of polished brass; these are often
plated with gold or platinum to avoid corrosion. Recently weights of
stainless steel have been introduced. The fractional weights, from
05 g. downwards, are made of platinum, gold, aluminium,or tantalum;
they are usually square in shape and have one corner turned up to
. facilitate handling. The nominal mass is stamped on each weight,
the numbers indicating grams, fractions of a gram, or milligrams.
Duplicate and triplicate weights are stamped with one or two asterisks.
For handling the weights, a pair of forceps, frequently tipped with
ivory or some similar material, is provided: on no account shsmld
weights be touched with the fingers.
All weights should be calibrated (Section II, 8). The values may
change with time, and it is advisable to recalibrate the weights at least
once a year.
II, 5. Care and use of the balance.-l. The balance should be placed
upon a firm foundation which is as free from mechanical vibratio~as
possible. The ideal foundation is a concrete or stone slab resting uI'on
brick piers, which are either sunk into the ground or, if this is
._ not practicable, into the stone or concrete flooring beneath the floor-
, boards of the laboratory. If this is not possible, the balance should be
placed upon a stout table or shelf and protected, when necessary, by
shock-absorbing media, such as cork mats or sheet rubber under the
table: anti-vibration tables, designed for balances, are available from
most laboratory suppliers. It is best to keep the balance in a room
separate from the laboratory in order to protect it from fumes. Us
position should be such that the two arms are at the same temperature.
Hence the balance should not be placed with one side near a window or
radiator, or in direct sunlight, or in a position where it is likely to come
into contact with draughts.
The balance should be level. This adjustment may be made with
the aid of the levelling-screws.
2. When not in use, the balance beam and the pan supports should
be raised so as to protect the agate prisms and planes. The doors of
the balance should be kept closed as much as possible.
3. To release the balance, the beam and pans should be lowered very
carefully and set swinging by fanning one pan gently with the hand, or
j>y carefully turning the arresting screw. The beam should never be
Technique of Quantitative Analysis 155
set swinging by touching the pan with the forceps or with some other
object, or by suddenly lowering it upon its prism edges.
4. Objects to be weighed must be allowed to attain the temperature
of the balance before weighing is attempted, otherwise the air currents
produced inside the balance case may introduce serious errors. If the
object has been heated, sufficient time must be allowed for cooling.
The time required to attain the balance-room temperature varies with
the size, etc., of the object, but as a rule 30-40 minutes is sufficient.
5. Weights and the object to be weighed should always be placed in
the centre of the pans.
6. During a weighing or upon any occasion when objects are being
added to or removed from the pans, both the beam arrests and the
pan supports must be rais,d so as' to protect the prism-edges from
injury. Always close the lalance case when using the rider.
7. No chemicals or objects which might injure the balance pans
should ever be placed directly upon them. Substances must be
weighed upon suitable containers, such as watch glasses, small beakers,
weighing-bottles, or crucibles. Liquids and volatile or hygroscopic
solids must be weighed in a tightly closed vessel, such as a stoppered
weighing-bottle.
8. The balance must not be overloaded (see Section II, 3 (d)).
9. Weights should be handled only with the forceps provided with
the box.
10. Nothing must be left on the pans when the weighing has been
completed. If any substance is spilled accidentally upon the pans or
upon the floor of the balance-case, it must be removed at once. The
pans should be lightly brushed periodically with a camel-hair brush to
remove dust which may have collected.
11. If the balance requires adjustment, the teacher should be notified
immediately.
~
,,
,
,
,
,
" 3,75 x
,
,
I .o(~~-325x---> I
Ic:- .. - .. - - - - - - Ix - - - - --~
(a) ( b)
FIG. II, 6, 2.
,.
I
(a) (b)
FIG. II, 7, 1.
The density of the air will depend upon the humidity, the temperature,
and the pressure. For an average humidity (50 per cent) and average
conditions of temperature and pressure in a laboratory, the density of
the air will rarely fall outside the limits 0'001l and 0-0013 g./mI. It is
therefore permissible for analytical purposes to take the weight of I
mI. of air as 00012 g.
Since the difference between Wv and Wa does not usually exceed 1 to
2 parts per thousand, we may write:
= Wa + k W a/l000 (3)
where k = 120 (~
db
- _!_)
84
The values of k for da = 0-0012 and dw = 84 have been calculated and
164 Quantitative Inorganic Analysis
are collected in the following table. If a substance of density db
weighs Wa grams in air, then WI<' k milligrams are to be added to the
weight in air in order to obtain the weight in vacuo. The correction is
positive if the substance has a density lower than that of brass, and
negative if the density of the substance is greater than that of brass.
k. k. k.
db' I I dh - I ) db'
05 +226 19 +049 no -003
06 +188 20 +048 120 -0'04
07 +157 25 +034 130 -005
08 +136 30 +026 140 -006
09 +1-19 35 +020 150 -006
10 +106 40 +016 160 -0'07
11 +095 45 +013 170 -0'07
12 +086 5-0 +0-10 18-0 -0-08
13 +078 . 5-5 +0-08 190 -008
1-4 +0-72 6-0 +006 20-0 -0-08
1-5 +066 7-0 +0-03 21-0 -0-09
16 +0-61 8-0 +0-01 220 -0-09
. 17 +056 90 -0'01 230 -009
18 +052 100 -002 240 -009
I
I Sensi Differ.
Relative Ideal Correc
Tare Nominal Wt. Rest tivity Values if Cali tion in
on Left on Right Pan. Point. Div. ence 001 g. bration mg.
Pan. mg. in g. Correct. Value.
02 01 + 01* 92 (02008)
02 107 -00003 02005 02008 -03
5 2,1,1*,1** 80 (50191)
5 92 -00002 50189 50193 -04
50 20,10,10*,5,2
1,1*,1** 120 36 (501910)
50 85 +00010 501920 501925 -05
\
Class A. Class B.
Denomination.
Accuracy of
Certificate (mg.). Tolerance (mg.). Tolerance (mg.).
100 g. 01 1 5
50 g. 005 05 2
20
10
g.
g.
002
002
02
01
I
05
I
5 g. 001 01 05
2 g. 001 01 05
1 g. 001 01 05
500 mg. 001 01 05
I
200 mg. : 001 01 02
100 mg. 001 01 02
50 mg. 001 005 02
20 mg. 001 005 02
10 mg. I
001 005 02
5 mg. 001 005 02
2 mg.
I mg.
: 001
001
005
005
02
01
,
I
The U.S. Bureau of Standards at Washington recbgnises three classes
of weights, M, S, and S-2. Class M weights are employed as primary
reference standards against which all weights may be checked and are
of one-piece construction. Class S weights are used for routine accurate
work in scientific laborato.des; they may be of two-piece construction
with a screw knob, so that exact adjustment of mass may be made by
placing a small piece of a suitable metal within the cavity beneath the
knob. The tolerances for Class M and Class S weights are identical.
Class S-2 weights have tolerances five times those permitted for Class
S weights, and are adequate for most student requirements. The
precision of correction and tolerances are collected in Table V.
TABLE V.-U.S. BUREAU OF STANDARDS-ANALYTICAL WEIGHTS
. FlO. II, 9, 1.
FIG. II, 9, 2.
FIG. II, 9, 3.
The upper left-hand knob controls the 100-g. weight: the lower left-
hand knob controls tens of grams; the upper right-hand knob deals
with grams, and the lower right-hand knob controls tenths of a gram.
The counter in the centre of the control panel automatically records
the weight to the nearest decigram. Upon now operating the pan-
release lever on the left of the balance, the figures to the nearest tenth
of a milligram automatically appear, by optical projection, on the scale.
An enlarged "mechanical and optical weight scale with vernier" is
shown in Fig. II, 9, 6: the weight shown is 1624312 g. The zero
point is determined by turning a knob', situated in the right-hand side
of the instrument, which moves a plane prism in the optical system.
The zero line of the projected scale and the zero line of the vernier can
be made to coincide in this manner. It is claimed that the entire
sequence of operations, including the placing of the object on the
174 Quantitative Inorganic Analysis
balance-pan, requires 21 seconds in the hands of a technician with
limited experience in handling the new balance.
It must be pointed out that the balances described under D and E
suffer from the disadvantage that it is impossible to provide a tare of .
FIG. II, 9, 5.
FIG. II, 9, 6.
equal volume for the object being weighed: this is of little moment
when dealing with routine weighings by difference.
F. Semimicro balances. These are balances with a sensitivity of 001
mg. and are becoming increasingly popular for many types of analytical
work in which minute quantities of materials are involved. The
Oertling " semimicro chemical balance, No. 141" (" Aperiodic Micro
Balance " ), illustrated in Fig. IJ, 9, 7, is a typical example of a high-
grade instrument. The maximum load is 30 g. Rapid weighing is
ensured by air damping. Fractional weights, up to a total of 009 g.,
. are added by means of a mechanical-loading device fitted to the right-
hand side of the case; it can be turned in both directions and is direct
ieading. The rider bar is serrated into ten parts from " 0 " on the
Technique of Quantitative Analysis 175
left to " 10 " on the right for use with a 5-mg. rider adjusted at zero.
The illuminated graticule is divided " 0- 100" with zero reading at
" 0 ": one division represents 001 mg. A total displacement of 01 g.
is thus provided for without opening the case: larger weights are
FIG. II, 9, 7.
Ii
(a) (b)
the burner up or down and thus allowing more or less air to enter through
the holes at the base. The Pittsburgh universal burner * (sometimes
termed a Tirril burner) and one of the Fletcher burners t are of this
type. A temperature of 1050-1150 C. in a covered platinum crucible
or 600-700 C. in a covered porcelain crucible can be attained with these
burners.
With a Maker burner t a temperature of 1100-1200 C. is said to be
reached in a covered platinum crucible and 800-900 C. in a covered
porcelain crucible. The volume of air passing through a fully aerated
ordinary Bunsen burner is about 25 times the volume of the gas; for
the complete combustion of coal gas about 6 volumes of air are neces-
sary. If a mixture of coal gas and air in the latter proportions were
ignited at an ordinary Bunsen burner, the flame would" strike back"
and burn at the bottom of the tube. In the M6ker burner (Fig. 11,10,
1, a) the holes for the admission of air are large enough to pass sufficient
air for the complete combustion of the gas, and the tube is narrowest
near the base and widens out near the top, thus resulting in a more
* Manufactured by the Fisher Scientific Company, 711-723 Forbes Street, Pittsburgh,
Pa., U.S.A.
t Manufactured by Fletcher, Russell and Co., Ltd., Palatine Works, Warrington, .
England.
Technique of Quantitative Analysis 177
perfect mixing of the gas with air; a nickel grid is fitted into the top of
the burner in order to prevent the flame striking back. The gas burns
in many small flames, with the top of each inner reducing cone about
1 mm. above the top of the burner. The numerous small flames com-
bine to give a very hot and highly concentrated flame, which is oxidising
in character except below the tips of the tiny flames; the maximum
temperature is attained just a little above the small flames, i.e., about
2-3 mm. from the top of the burner. The burner is used for the
ignition of pre~pitates that require a high temperature for conversion
into a weighable form, and also for some fusions. A blow-pipe flame
or "blast lamp" is sometimes used for these purposes, but in most
cases equally satisfactory results are obtained with the Meker burner.
An improved form of the ordinary Meker burner (e.g., in the Fisher
"high-temperature" burner, Fig. 11,10,1, b) contains an arrangement for
adjusting both the gas and air' supplies as in the Pittsburgh universal
burner already described.
The" Amal" burner * attempts to combine the chief features of the
improved Bunsen burner and the Meker burner. The flame can be
turned down very low without flashing back, and it also furnishes a
very h?t flame. This is a very useful burner, but is comparatively
expensIve.
B. Wash bottles. A wash bottle is a flat-bottomed flask fitted up to
deliver a fine stream of distilled water or other liquid for use in the
transfer and washing of precipitates. A convenient
size is a 500-750-ml. flask of Pyrex or other resis-
tance glass; it should be fitted up as shown in
Fig. II, 10,2. A rubber bung is used, and the glass
tubes above the bung should be in the same straight
line and lie in the same plane. The jet should
deliver a fine stream of water; a suitable diameter
of the orifice is 1 mm. All glass tubing must be
rounded in the Bunsen flame after cuttiag. Thick
string, asbestos string, thin sheet cork, or other
insulating material, held in place by copper wire,
should be wrapped round the neck of the flask in
order to protect the hand when hot water is used.
Asbestos paper is best applied wet and allowed to FIG. II, 10, 2.
dry overnight : there is sufficient adhesive material
in the paper to make it cling tightly. In order to protect the mouth from
scalding by the back rush of steam through the mouth-piece when the
blowing is stopped, it is convenient to use a three-holed rubber stopper;
a short piece of glass tubing open at both ends is inserted in the
third hole. The thumb is kept over this tube whilst the water is being
blown out, and is removed immediately before the mouth pressure is
released.
All-glass wash bottles, fitted with ground-glass joints, can be pur-
chased. They should be used with organic solvents that attack rubber.
C. Distilled water. Distilled water must be employed in all analytical
work. Various forms of still are in common use. It is important that
the vessel containing the boiling water, which may be of almost any
material, should be so separated from the condenser that there is little
or no danger of spray entering the latter. The condenser should be of
* Manufactured by Amal, Ltd., Holford Works, Perry Bar, Birmingham, England.
178 Quantitative Inorganic AnalY8is
pure tin or, if this is not possible, be heavily plated with tin. The dis-
tilled water thus prepared may contain small quantities of dissolved
ammonia and carbon dioxide. For water analysis and other purposes
requiring highly purified water, the distilled water should be re-distilled
from alkaline potassium permanganate, and the head and tail fractions
rejected; most of the dissolved ammonia is removed by this process.
The most convenient method for the preparation of highly purified
water (the so-called conductivity water) is to employ a mixture of two
ion-exchange resins, a strong-acid resin and a strong-base resi'l. The
strong-acid resin will remove cation impurities in the water supply and
exchange them for hydrogen ions, and the latter ions are immediately
neutralised by the basic resin: anions are removed by the strong-base
resin in the same way. An intimate mixture of 3 parts of Permutit
"D.e-acidite F" and 1 part of Permutit "Zeo-Karb 315,"* with a
volume of about 200 ml., is placed in a Pyrex tube of 1 in. diameter
and 24 in. long. The column is washed with distilled water until the
conductivity of the water emerging is the same as that entering; if this
process requires excessive quantities of water, it is advisable to allow
the mixture of resins to stand in contact with distilled water for about
24 hours and continue the washing, when the conductivity will fall
rapidly. Such a column will give about 200 litres of conductivity water
of specific conductivity 0,1-0,2 X 10-6 reciprocal ohms: the specific
conductivity of this water rises to that of " equilibrium" water (08-
10 X 10-6 reciprocal ohms) on exposure to air unless precautions are
taken to exclude carbon dioxide. Similar results are obtained with the
Rohm and Haas resins" Amberlite IR-120" and" Amberlite IRA-
400," t which must be freshly regenerated; a volume of 30-50 ml. of
total resins, packed in a Pyrex tube of 30 cm.length and fed with boiled-
out distilled water, will produce many hundreds oflitres of conductivity
water (C. W. Davies and C. H. Nancollas, 1950).
D. Glassware. In order to avoid the introduction of impurities
during analysis, resistance-glass apparatus should be employed. For
most purposes Pyrex glass (a boro-silicate glass) is to be preferred.
Chance's Hysil glass is also satisfactory. As a rule glassware should
not be heated with a naked flame; a wire gauze, preferably with an
asbestos centre, should be interposed between the flame and the glass
vessel.
The most satisfactory beakers for general use are those provided
with a spout. The advantages of this form are: (a) convenience of
pouring, (b) the spout forms a convenient place at which a stirring rod
may protrude from a covered beaker, and (c) the spout forms an outlet
for steam or escaping gas when the beaker is covered with an ordinary
clock glass. The size of a beaker must be selected with due regard to
the volume of the liquid which it is to contain. The most useful sizes
are from 250 to 600 ml. For evaporations with high-boiling-point
liquids, e.g., sulphuric acid, the shallo}\', squat type of beaker (e.g,
Cnance's Baco type) is preferable.
Conical (or Erlenmeyer's) flasks of 200-500-ml. capacity find many
applications, for example, in titrations.
* Manufactured by The Permutit Company, Ltd., Gunnersbury Avenue, London,
W.4, England; the regenerated resins should be used.
t Manufactured by Rohm and Haas Company, The Resinous Products Division,
Washington Square, Philadelphia 5, Pa., U.S.A.: supplied in Great Britain by British
Drug Houses Ltd., Poole, Dorset.
Technique of Quantitative Analysis 179
Funnels should ellclose an angle of 60. The most useful sizes for
quantitative ~nalysis are those with diameters of 55, 7, and 9 cm. The
stem should have an internal diameter of about 4 mm. and should not be
more than 15 cm. long. For filling burettes and transferring solids to
graduated flasks, a short-stem, wide-necked funnel is useful.
E. Porcelain apparatus. Porcelain is generally employeQ_ for opera-
tions in which hot liquids are to remain in contact with the vessel for
prolonged periods. It is usually considered to be more resistant to
solutions, particularly alkaline solutions, than glass, although this will
depend primarily upon the quality of the glaze. Shallow porcelain
basins with lips are employed for evaporations. Casseroles are lipped,
flat-bottomed porcelain dishes provided with handles; they are more
convenient to use than dishes.
Porcelain crucibles are very frequently utilised for igniting precipitates
and heating small quantities of solids because of their cheapness and
their ability to withstand hig~ temperatures without appreciable
change. Some reactions, such as fusion with sodium carbonate or
other alkaline substances, and also evaporations with hydrofluoric acid
cannot be carried out in porcelain crucibles owing to the resultant
chemical attack. A slight attack of the porcelain also takes place with
pyrosulphate fusions.
F. Fused-silica apparatus. Two varieties of silica apparatus are
available commercially, the translucent and the transparent grades.
The former is much cheaper and can usually be employed instead of the
transparent variety. The advantages of silica ware are: (a) its great
resistance to heat shock because of its very small coefficient of expansion,
(b) it is not attacked by acids at a high temperature, except by hydro-
fluoric acid and phosphoric acid, and (c) it is more resistant to pyro-
sulphate fusions than is porcelain. The chief disadvantages of silica
are: (a) it is attacked by alkaline solutions and particularly by fused
alkalis and carbonates, (b) it is more brittle than ordinary glass, and
(c) it requires a much longer time for heating and cooling than does,
say, platinum apparatus.
G. Platinum apparatus. This is discussed fully in Section II. :rI.
Mention may, however, be made here of the resistance of platInUm
ware to fusions with sodium and/or potassium carbonate, and to evapora-
tions with hydrofluoric acid and other single acids. A great advantage
is its high thermal conductivity: a red-hot platinum crucible placed in
a desiccator to cool is ready for weighing after about 25 minutes. .
H. Silver apparatus. The chief uses of silver crucibles and dishes
in the laboratory are in the evaporation of alkaline solutions and for
fusions with caustic alkalis; in the latter case, the silver is slightly
attacked. Silver melts at 960 C., and care should therefore be taken
when it is heated over a bare flame.
I. Nickel ware. Crucibles and dishes of nickel are employed for
fusions with alkalis and with sodium peroxide. In the peroxide fusion
a little nickel is introduced, but this is usually not objectionable. No
metal entirely withstands the action of fused sodium peroxide. Nickel
oxidises in air, hence nickel apparatus cannot be used for operations
involving weighing.
3'. Iron ware. Iron crucibles may be substituted for those of nickel
in sodium peroxide fusions. They are not so durable, but are much
cheaper.
180 Quantitative Inorganic Analysis
K. Bakelite apparatus. This synthetic resin is unaffected by hydro-
fluoric acid at the ordinary temperature. Bakelite funnels, measuring
cylinders, etc., are available for use with this acid.
L. Stirring-rods. These are made from glass rod 3-5 mm. in diameter,
cut into suitable lengths. Both ends should be rounded by heating in .
the Bunsen or blowpipe flame. The length of the stirring-rod should
be suitable for the size and the shape of the vessel for which it is
employed, e.g., for use with a beaker provided with a spout, it should
project 3-5 cm. beyond the lip when in a resting position.
A stirring-rod of convenient size should be provided with a short.
piece of rubber tubing fitted tightly over one end. This is the so-called
policeman; it is used for detaching particles of a precipitate adhering
to the side of a vessel which cannot be removed by a stream of water
from a wash bottle; it should not, as a rule, be employed for stirring,
nor should it be allowed to remain in a solution.
M. Boiling-rods. Boiling liquids and liquids in which a gas, such as
hydrogen sulphide, sulphur dioxide, etc., has to be removed by boiling
can be prevented from superheating and" bumping" by the use of
..
(A) (8)
FIG. II, 10, 3. FIG. II, 10, 4.
a boiling-rod (Fig. II, 10, 3). This consists of a piece of glass tubing
closed at one end and sealed approximately I cm. from the other end;
the latter end is immersed in the liquid. When the rod is removed, the
liquid in the open end must be shaken out and the rod rinsed with a
jet of water from a wash bottle. This device should not be used in
solutions which contain a precipitate.
N. Desiccators. An ordinary Scheibler-type of desiccator (Fig..
II, 10,4, A) is used for maintaining a dry atmosphere in which to place
objects that might be affected by moisture or carbon dioxide. The
drying agent (usually calcium chloride in elementary work) is placed
in the lower compartment, and the upper compartment is fitted up for
the accommodation of crucibles, weighing-bottles, etc. For small
desiccators, a silica triangle with wire ends is bent so that the ends are
perpendicular to the plane of the triangle, and then the wire ends
spread out sufficiently so that they press against the walls and floor of
the compartment and are thus held firmly into position. With large
desiccators, a porcelain plate on feet (Fig. II, 10, 4, A), provided with
apertures for crucibles, etc., is to be preferred: it should be wedged
into the sides, if necessary, with cork or some other material. The
ground edge of the desiccator should be lightly coated with white
vaseline or a special grease in order to make it air-tight; too much grease
may permit the lid to slide.
Technique of Quantitative Analysis 181
When a hot object is placed in a desiccator, about 5-10 seconds
should elapse for the air to become heated and expanded before putting
the cover in place. In removing the object, the cover should be slid
open very gradually in order to prevent any sudden inrush of air due
to the partial vacuum Which exists owing to the cooling of the expanded
gas content of the desiccator and to desiccation, and thus prevent the
precipitate being blown out of the crucible.
A desiccator is also employed for thorough drying of solids for
analysis and other purposes. A very convenient type is portrayed in
Fig. II, 10, 4, B, a form of "vacuum" desiccator; these are made of
thick glass and should be tested by the manufacturers for use with a
high vacuum. Large surfaces of the solid can be exposed, and the
whole can be evacuated; drying is thus much more rapid than in the
ordinary Scheibler desiccator. Pyrex-glass desiccators, both plain and
for " vacuum" work, are marketed: these are made of heavy Pyrex
glass, and will withstand greater mechanical and thermal shock than
those made of soda glass. Phoenix-glass desiccators (a heat-resisting
glass)* are cheaper than those of Pyrex glass, and are satisfactory for
general student use; the parts are standard, so that a broken cover, for
example, can be readily replaced.
Attention is directed to, an all-aluminium desiccator (the Fisher
" desicooler") which is now marketed.t It is fitted with a shelf
containing three holes to accommodate three sizes of crucible, and
employs activated alumina as the desiccant (corrosion of the aluminium
may occur with other desiccants). The charge of about 60 g. of activated
alumina may be reactivated when exhausted by simply heating to
0
175 C. This desiccator should prove useful for general students'
use since it is unbreaka~le and inexpensive. Larger aluminium desic-
cators (45 in. and also 8 in. diameter) of more robust construction are
also available.
The most commonly used desiccant is granular, fused calcium chloride;
the 3-8-mesh size is very suitable, but the fused lumps are often em-
ployed on account of cheapness. In point of fact, the so-called an-
hydrous calcium chloride (the hydrated crystalline variety is useless
for this purpose) is not a very efficient drying agent (it usually contains
about t molecule of water), but it is satisfactory for most purposes.
Phosphorus pentoxide is the most powerful common desiccant known;
it should be used only when it is absolutely necessary, and must be
renewed as soon as a crust forms over its surface. Concentrated
sulphuric acid is better than calcium chloride; it should be poured
over pumice or broken glass or glass beads, and should not cover the
solid completely, thereby reducing the danger of splashing of the liquid
on to the bottom of objects in the desiccator: the acid must be replaced
as soon as it shows signs of darkening. Re-sublimed iodine must not
be dried over sulphuric acid. Anhydrous magnesium perchlorate
(anhydrone or dehydrite) and magnesium perchlorate dihydrate have
found wide application; they are comparatively expensive for use in
desiccators, but the former is extensively employed in the quantitative
absorption of water. Anhydrone rivals phosphoric oxide in its power
of desiccation; it can absorb about 50 per cent of its weight of water,
and can be regenerated by suitable means. Anhydrous calcium
* Supplied by Jencons (Scientific), Ltd., Rosebank Way, Acton, London, W.3.
t Obtainable from the Fisher Scientific Co., Pittsburgh, Pa., U.S.A.
182 Quantitative Inorganic Analysis
sulphate (marketed in a porous form as drierite) is a very useful and
relatively inexpensive desiccant. The relative efficiencies of various
drying agents will be evident from the data presented in Table VI.
fJB
d (C)
.
I
I
constructed entirely of hard tool steel. One or two
small pieces are placed in the mortar, and the pestle
inserted into position; the latter is struck lightly with
a hammer until the pieces have been reduced to a
~
coarse powder. The whole of the hard substance may
be treated in this manner. The coarse powder is then
ground in an agate mortar in small quantities at a
time. A mortar of mullite * is claimed to be superior
to one of agate: mullite is a homogeneous ceramic FIG. II, 15, 1.
material that is harder, more resistant to abrasion
and less porous than agate. A synthetic sapphire mortar and pestle *
(composed essentially of a specially prepared form of pure aluminium
oxide) is marketed; it is extremely hard (comparable with tungsten
carbide) and will grind materials not readily reduced in ceramic or
metal mortars.
II, 16. Solution of the sample.-Most of the synthetic samples
employed in the teaching of elementary quantitative analysis are
s91uble in water or in dilute acids. Naturally occurring minerals and
ores, various alloys, etc., must usually be treated with various reagents
in order to bring them into solution. In such cases, the qualitative
analysis will have revealed the best procedure to adopt. Each case
must be considered on its merits; no attempt at generalisation will
therefore be made. We can, however, discuss the experimental
technique of the simple process of solution of a substance in water or
in acids, and also of insoluble substances.
The sample is weighed out into a beaker, and the beaker immediately
covered with a clock glass of suitable size (its diameter should not be
more than about 1 cm. larger than that of the beaker) with its convex
side facing downwards. The beaker should have a spout in order to
provide an outlet for the escape of steam or gas. The solvent is then
added by pouring it carefully down a glass rod, the lower end of which
rests against the wall of the beaker; the clock glass is displaced some-
what during this process. If a gas is evolved during the addition of
the solvent (e.g., acids with carbonates, metals, alloys, etc.), the beaker
must be kept covered as far as possible during the addition. The
reagent is then best added by means of a pipette or by means of a
funnel with a bent stem inserted beneath the clock glass at the spout
of the beaker; loss by spirting or spray is thus prevented. When
the evolution of gas has ceased and the substance has completely
dissolved, the under side of the clock glass is well rinsed with a stream
of water from a wash bottle, care being taken that the washings fall
on to the side of the beaker and not directly into the solution. If
warming is necessary, it is usually best to carry out the entire operation
of solution in a conical (Erlenmeyer) flask with a small funnel in the
mouth (Fig. II, 16, I, a); loss of liquid by spirting is thus prevented
and the escape of gas is not hindered.
* Available from the Fisher Scientific Co., Pittsburgh, Pa., U.S.A.
190 Quantitative Inorganic Analysis
It may often be necessary to reduce the volume of a solution, or
sometimes to evaporate it completely to dryness. Wide and shallow
vessels are most suitable, since a large surface is thus exposed and
evaporation is thereby accelerated. We may employ shallow beakers of
resistance glass (e.g., Chance's "Baco " beakers), Pyrex evaporating
dishes, porcelain basins or casseroles, silica or platinum basins; the
material selected will depend upon the extent of attack of the hot
liquid upon it and upon the constituents being determined in the
subsequent analysis. Evaporations should be carried out on the steam ~
bath or upon a low-temperature hot plate; slow evaporation is pre-
ferable to vigorous boiling, since the latter may lead to some mechanical
loss in spite of the precautions to be mentioned below. During evapora-
tions, the vessel must be covered by a clock glass of slightly larger
diameter than the vessel, and supported either on a large all-glass
triangle or upon three small U-rods of glass hanging on the rim of the
container. A device known as Fisher's "speedy-vap" beaker cover *
(Fig. II, 16, 1, b) is an improvement on the ordinary watch or clock glass
and is of value for simple evaporations. It consists of a clock glass of
resistance glass provided with three fused-on glass ribs. Needless to
say, at the end of the evaporation the sides of the vessel, the lower side
r0
\d,
(b) (c)
(a)
~, '
FIG, II, 16, 1.
of the clock glass (simple or modified forms), and the triangle and gla~s
hooks (if employed) should be rinsed with distilled water into the vessel.
For evaporation at the boiling point either a conical flask with a
short funnel in the mouth or a round-bottomed flask inclined at an
angle of about 45 (Fig. II, 16, 1, c) may be employed; in the latter the
drops of liquid, etc., thrown up by the ebullition or by effervescence
will be retained by striking the inside of the flask, whilst gas and vapour
will escape freely.
Substances which are insoluble or only partially soluble in acids are
brought into solution by fusion with the appropriate reagent. The most
commonly used fusion reagents, or fluxes as they are called, are anhy-
drous sodium carbonate either alone or, less frequently, mixed with
potassium nitrate or sodium peroxide, potassium, or sodium pyrosul-
phate, sodium peroxide, sodium or potassium hydroxide. The flux
employed will depend upon the nature of the insoluble substance. The
vessel in which fusion is effected must be carefully chosen; platinum
crucibles are employed for sodium carbonate and potassium pyro-
sulphate; nickel or silver crucibles for sodium or potassium hydroxide;
nickel, gold, silver, or iron crucibles for sodium carbonate and/or sodium
peroxide; nickel crucibles for sodium carbonate and potassium nitrate
(platinum is slightly attacked). To carry out the fusion, a layer of
* Marketed by the Fisher Scientific Co., of Pittsburgh, U.S.A.
Technique of Quantitative Analysis 191
the flux is placed at the bottom of the crucible, and then the intimate
mixture of the flux and the finely-divided substance added; the crucible
should be about half-full, and should, generally, be kept covered during
the whole process. The crucible is very gradually heated at first, and
the temperature slowly raised to the required temperature. The final
temperature should not be higher than is actually necessary; any
possible further attack of the flux upon the crucible is thus avoided.
When the fusion, which usually takes 30-60 minute~, has been com-
pleted, the crucible is grasped by means of the crucible tongs (see
Section II. 37) and gently rotated and tilted so that the molten material
distributes itself around the walls of the container and solidifies there
as a thin layer. This procedure greatly facilitates the subsequent detach-
ment and solution of the fused mass .. When cold, the crucible is
placed in a casserole, porcelain dish, platinum basin, or Pyrex beaker
(according to the nature of the flux) and covered with water. Acid is
added, if necessary, and the vessel is covered with a clock glass (pre-
ferably of the "speedy-vap" type), the temperature raised to 95-100 C.,
and maintained until solution is achieved.
Full experimental details for effecting fusions with sodium carbonate
and potassium pyrosulphate are given in the analysis of silicates, felspar,
etc., in Chapter IV.
Degrees C. 5 10 15 20 I 25 1 30
Note.-For the calibration of flasks of capacity other than I lit.re, the corre-
sponding multiple or sub-mult.iple of the above values is t.aken_
II, 21. Pipettes.-Pipettes are of two kinds: (i) those which have one
mark and deliver a small, constant volume of
liquid under certain specified conditions (transfer
pipettes); (ii) those in which the stems are
graduated and are employed to deliver various
small volumes at discretion (graduated or measuring
pipettes). They are shown in Fig. II, 21, 1 as
a and c; type b is a useful form which is
employed for measuring out corrosive liquids,
the bulb preventing the entrance of liquid into 25 25
ml ml.
the mouth. Graduated pipettes are useful for 20
measuring out volumes ofliquids approximately; C.
they are not employed in exact work.
Transfer pipettes are constructed with capaci-
ties of 1, 2, 5, 10, 20, 25, and 50 ml.; those of
10, 25, and 50 ml. capacity are most frequently
employed. In using such pipettes, they are first
rinsed with the liquid, then filled by suction to
about 1-2 cm. above the mark, and the upper
end of the pipette is closed with the tip of the
dry index finger; any adhering liquid is wiped
from the outside of the lower stem. The liquid
is allowed to run out slowly by slightly relaXing (a) (b) (e)
ml mI
-:::- :::
=
= =
-= =
-
=
=
(Fig. II, 22, 3), is inexpensive: each burette is held in place by means
of three arms, the centre one under spring tension; a burette is removed
by pressing the central lever in front of the holder; it is made largely
of steel and is finished in baked black enamel.
The mode of use is as follows. The clean, empty burette is fixed into
a suitable stand and clamped vertically. About 10 ml. of the solution
to be employed is poured into it so as to wet the whole internal surface,
and is then run completely out; this rinsing is repeated. The buretto
is then filled to a little above the highest graduation; if a short funnel
is used it must be removed immediately after the filling. The liquid
is then allowed to flow out until the lowest point of the meniscus just
touches this graduation; the jet must of course be completely full of
liquid. To read the position of the meniscus, the eye must be at the
* Manufactured by Fisher Scientific Co., 717 Forbes Street, Pittsburgh, Pa., U.S.A.
Technique of Quantitative Analy8~8
same level as the meniscus, in order to avoid errors due to parallax. In
the best type of burette, the graduations are carried completely round
the tube for each ml. and half-way round fot' the other graduation
marks: parallax is thus easily avoided. To aid the eye in reading the
fiSHER
@,
._
outlined against the white background (Fig. II, 22, 4);* the level of
the liquid can then be accurately read. Fot' all ordinary purposes
readings are made to 005 ml.; for precision W()rk readings to 001-02
ml. (by estimation with the aid of a lens) should be made.
* A celluloid black and white disc, which can be slipped over the burette is available
commercially (e.g., "Fisher" burette meniscus holder, "Baird and Tatlock" burette
reader, etc.).
_"
~ ~.':.
200 Quantitative Inorganic Analysis
The so-called Schellbach burette, which contains a whit~ enamelled
band, with central blue ribbon, fused vertically at the back of the
burette tube, was originally intended to improve the ease of reading
the level of the liquid and also to eliminate parallax. Its use in
practice is not, however, very satisfactory, and hence cannot be
recommended.
As a general rule, it is advisable to use the zero mark each time. It
has been established that practically no after-drainage takes place in a
burette if the rate of outflow does not exceed a certain speed. If the
speed is exceeded, owing to the jet being too large, then drainage takes
place for several minutes. The limits for
the time of outflow with the tap fully open
and the jet not in contact with the receiv-
ing vessel are given in connexion with
the N.P.L. "Class A" tests in a subse-
quent paragraph. A burette should be
selected which conforms to these limits.
The drop adhering to the jet after the liquid
has been discharged is removed by bring-
ing the side of the receiving-vessel into
FIG. II, 22, 4. contact with the jet. When not in use,
burettes should be well rinsed with
distilled water and covered with a short inverted test-tube to keep out
dust, or they may be inverted in the burette stand, jet uppermost.
Burettes fitted with rubber and a pinchcock are used for alkaline
solutions and as cheap substitutes for glass stopcock burettes; they
cannot be employed for such solutions as potassium permanganate and
iodine, which attack rubber. The use of any form of burette other
than that fitted with a glass stopcock is not recommended, for the
following reasons: (i) some of the liquid may attack the rubber,
and (ii) it is impossible to see whether the air has been completely dis-
placed in the rubber tube. Alkaline solutions, including those of
caustic alkalis, may be used with glass taps, but the burettes must be .
emptied and washed immediately after use, otherwise the taps are
liable to stick. 'Where the use of alkaline solutions in a burette is a
routine process, it is best to utilise a nickel or silver stopcock.
Lubricants (or greases) for glass stopcocks. The simplest lubricant is
either pure vaseline or a mixture of pure vaseline and resin cerate .
.; A " soft" grease may be prepared by thoroughly mixing, by melting
and stirring, 1 part of beeswax and 3 parts of pure vaseline. A" hard"
grease is obtained by adding 1 part of soft black rubber in small pieces
to the latter mixture, heating to 140-150 C., and stirring continuously
until thoroughly incorporated.
An excellent lubricant (Shepherd, 1931), which is particularly suitable
for gas-analysis apparatus, is obtained from 6 parts of rubber (pale
crepe, freshly milled, and free from dirt and lint), 7 parts of white
vaseline, and 1 part of paraffin wax, m.p. 40-45 C. The vaseline and
paraffin wax are melted in a large porcelain casserole, and the rubber is
added in several portions. The mixture is placed in a thermostated
oven or in an air-bath (Section II, 12F; first paragraph) and stirred
continuously for 190 hours at 155-165 C. It is then transferred to
2-oz. ointment jars and chilled in ice immediately, care being taken to
prevent condemmtion of water on the grease.
Technique of Quantitative Ana~y"~,,
Excellent lubricants may be purchased. * The Dow-Corning
" silicone" lubricant has many desirable properties and may be
strongly recommended.
The objects of adequate lubrication of the stopcock are to prevent
sticking or "freezing." The plug of the stopcock is removed from the
barrel, and the lubricant is applied lightly to the narrow portion of the
barrel of the tap and to the wide portion of the plug, taking care that
it does not reach the bore. Upon inserting the plug and turning it in
the barrel several times, a uniform film of grease will be distributed in
the ground joint. The stopper may be held in position by a rubber
band or other suitable device. The use of a stopper tie (Fisher), which
prevents loss or interchange of the plug, is recommended.
Calibration of a glass-stoppered burette. The burette is filled with
dichromate-sulphuric acid cleaning mixture and a beaker placed
beneath the burette. The burette is allowed to stand for one hour, but
preferably overnight. The solution is run out, and the burette rinsed
five or six times with distilled water. The stopcock and the inside of
the ground joint are then wiped dry; the stopcock is then smeared
lightly with a suitable lubricant as described in the preceding paragraph
and replaced into position. The burette is then clamped vertically and
filled with distilled water; the latter should have been standing for at
least an hour prior to use so as to be certain that it has acquired the
room temperature. The temperature of the water is noted. The air
in the jet is expelled by running out water from the burette. Two
methods are available for the actual calibration. The first is based
upon that employed at the National Physical Laboratory. The second
is due to Ostwald; it is very convenient to use, but is not accepted by
the N.P.L.
Method 1. The burette is filled with water to a short distance
above the zero mark, and water is slowly run out until the meniscus is
exactly on the zero mark. The drop of water adhering to the jet is
removed by bringing the jet into contact with the side of the beaker.
For reading the position of the meniscus to 0'01 mI., the device shown
in Fig. II, 22, 4 coupled, preferably, with a lens, may be employed. In
the better-quality burette in which the calibrations are carried com-
pletely round for the 1-mI. divisions and half-round for fractions of a
mI., errors due to parallax may be avoided by placing the eye so that
. the front and back of the graduation at the meniscus appear to coincide.
The burette is allowed to deliver freely, i.e., with the stopcock fully
open, into a clean, weighed Erlenmeyer (conical) flask of 100-150 ml.
capacity. When the meniscus of the water is approximately 1 cm.
from the line to be tested, the rate of outflow is reduced so that the
motion of the water surface is brought under complete control; the
meniscus is adjusted exactly on the mark. t No period of waiting for
drainage should be allowed. The drop adhering to the jet after the
. setting has been made is removed by bringing the side of the flask into
contact with the jet. The flask is then stoppered and weighed to the
nearest 001 g. This procedure is followed for each of the graduations
to be tested, e.g., at 5-mI. intervals, 5, 10, 15, 20, etc., or at 10-mI.
* A variety of lubricants is supplied by W. Edwards and Company, Worsley Bridge
Road, Lower Sydenham, London, S.E.26, and by the Fisher Scientific Co., Pittsburgh,
Pa., U.S.A.
t If this has been missed by a small amount, the volume is read to the nearest 00 I m!.
Quantitative Inorganic Analysis
intervals. The zero mark is always taken as the starting-point, since a
very small drainage error might take place between the readings and
effect the accuracy of the intermediate determinations. The whole
process should be repeated; the duplicate determinations should
agree within 2 centigrams. The volume actually delivered is calculated
from the weight of the water, and the volume of 1 g. of water at the
temperature of the calibration given in Table IX. The results should
be tabulated as follows:
CALIBRATION OF A BURETTE. (TEMPERATURE = - 0 C.)
000- 500 - i -- -
000-1000 - - -
000-1500 - - -
000-2000, etc. - - -
8
A
(:::fTII:===4I====!m' 0
(al (b)
Medium
Fast Speed. Speed. Slow Speed.
Retain Retain Retain
Filter-paper. Coarse Medium- Fine
Particles. sized Particles.
Particles.
Single acid (HCl) washed No. 31 No. 30 No. 32
Ash (mean) {Ii cm . .
cm. .
000020 g.
000030 g.
000021 g.
000031 g.
000022 g.
000033 g.
Hardened double acid washed No. 541 No. 540 No. 542
{ 9 em. 000004 g. 000004 g. 0000051 g.
II em. 000006 g. 000007 g. 0000076 g.
o
:
(a) (b)
until no fine fibres pass into the filtrate. It should be mentioned that
some analysts prefer to place a perforated porcelain plate (" Witt"
plate, Fig. II, 31, I, C) upon the asbestos mat to prevent its dislodge-
ment: a little more of the suspension is poured in to furnish enough
asbestos to barely cover the plate and to hold it in place. This procedure
is unnecessary if it be remembered that no liquid may be poured into
the crucible unless suction is being applied. Liquids should be poured
gently on to the centre of the mat down a stirring-rod: a jet of water
from a wash bottle should never be directed into the prepared crucible.
If these precautions are taken there is little danger that the mat will
become torn and allow the precipitate to pass through.
The crucible is placed on a small ignition dish or saucer or upon a
shallow-form Vitreosil capsule and dried to constant weight at the
same temperature as that which will be subsequently used in drying
the precipitate. For temperatures up to about 250 0 C. a thermo-
statically controlled electric oven should be used. For higher temp-
eratures, the crucible may be heated in an electrically heated muffle
furnace. If the latter is not available, it may be placed inside a larger
nickel crucible fitted with an asbestos ring (as in Fig. II, 31, 4), and the
larger crucible heated directly with a flame. In all cases the crucible is
allowed to cool in a desiccator (Section II, ION) before weighing. The
Technique of Quantitative Analysis 213
asbestos normally used for Gooch crucibles tends to lose weight above
283 0 C. (C. Duval, 1948), hence it is recommended that precipitates which
require heating above 280 C. should not be collected in Gooch crucibles.
Porous filtering crucibles (see below) may be employed.
II. 32. Munroe crucibles.-A platinum Gooch crucible, containing a
platinum mat, was devised by C. E. Munroe in 1888. The platinum
mat is prepared by igniting a layer of ammonium chloroplatinate,
moistened with alcohol, in the crucible. The chief features of such
crucibles are: resistance to chemical attack, rapidity of filtration,
retention of the finest precipitates, and possibility of heating to very
high temperatures. The platinum mat lasts almost indefinitely, for
the residues can be removed by any solution treatment which does not
dissolve platinum. On account of the high price of platinum, Munroe
crucibles are rarely employed in routine analysis; they find some
application for most exacting work, as in atomic-weight determinations.
II. 33. Crucibles fitted with permanent poroUS plates.-These possess
an advantage over Gooch crucibles in so far that no preparation of a
filter-mat is necessary. The best known are the sintered-glass crucibles.
, -
\\ 71
FIG. II, 31, 4. FIG. II, 33, 1.
They are made of resistance glass, for example, Pyrex, and have a
porous disc of sintered, ground glass fused into the body of the crucible
(Fig. II, 33, I). The fused-in fritted filter-disc can be obtained in
various degrees of porosity. Thus the aven~ge diameter of the pores
for plates numbered I, 2, 3, and 4 are 100-120 microns, 40-50 microns,
20-30 microns, and 5-10 microns respectively. No.4 is suitable for
very fine precipitates (such as barium sulphate), and No.3 for precipi-
tates of medium particle size. Two types of crucible find wide applica-
tion in quantitative analysis, the tall form and the low, wide form. A
crucible with a capacity of 30 ml. is satisfactory for most work.
The advantages of sintered-glass crucibles are: (i) they are made
entirely of glass, which is resistant to most chemical reagents with the
exception of hydrofluoric acid and hot, concentrated alkalis; (ii) they
can be driea to constant weight at 100-150 C.; and (iii) they are
readily cleaned. These crucibles can be heated to a temperature not
exceeding about 400 C. (Pyrex glass softens at about 610 C. and
permanent strain may be introduced at temperatures above 430 C.)
If heating above 150-200 C. is required, they should be placed in a
cold electric oven or furnace, heated to the appropriate temperature,
and allowed to cool to about 200 C. (in the furnace) before being removed
to a desiccator.
For temperatures above 200 C. Vitreosil filtering-crucibles * may be
* Manufactured by The Thermal Syndicate, Ltd., vValisend, England.
~14 Quantitative Inorganic Analysis
employed. These are similar to the sintered-glass crucibles, are
available in porosities I, 2, 3, and 4, but are made of Vitreosil pure fused
silica. They can be used up to 1000 C. and there is no danger of
cracking owing to sudden change of temperature. These crucibles are
attacked by phosphates, strong alkalis, and hydrofluoric acid, but are
otherwise very resistant to chemical reagents.
Another variety of crucible, which possesses many advantages over
the Gooch crucible, is the porous-porcelain filter-crucible. It consists of
a porcelain crucible, glazed inside and outside, with a porous porcelain
bottom. The 'Worcester Royal Porcelain Co.* manufactures one type
of crucible (Gooch form) in various sizes and an average pore diameter
of 5-10 microns; this meets most of the requirements of quantitative
inorganic analysis. It may be mentioned that crucibles with an average
pore diameter of 10-15 microns are also obtainable from this firm. It
is claimed that these filter-crucibles may be heated to temperatures as
high (1000 C.) as those possible for porcelain crucibles, but the temp- .
erature must be raised slowly, as the join between the porous disc and
the porcelain to which it is sealed may develop strain if heated suddenly.
A direct flame should be avoided: special ignition saucers are marketed
for heating the filter-crucibles up to a temperature of 1000 C. The
Selas Corporation of America t offer a wide range of porous filtering-
crucibles in porosities designated as XF, XFF, 10 and 01 corresponding
to average pore radii of 25, 10,2'2, and 1'5 microns respectively and to
maximum pore radii of 50, 20, 44, and 30 microns respectively. The
crucibles graded as 10 and 01 find the widest application in analytical
work. Selas crucibles are chemically inert, and are resistant to all
solutions which do not attack silica: they are attacked by hydrofluoric
acid, soluble fluorides, and strong alkalis.- They possess a high degree
of heat resistance, and are therefore capable of withstanding abnormal
heat shock. These crucibles may be heated to well over 1000 C., and
indeed will withstand direct heating by a powerful burner; in view,
however, of the possible action of the products of combustion upon the
precipitate, it is recommended that direct heating with a flame be
carried out in the special ignition dishes provided by the Selas Corpora-
tion. Porous porcelain filter-crucibles may also be heated in a larger
nickel crucible (Fig. II, 31, 4) or in a muffle furnace. These crucibles
are inexpensive, and therefore merit wide application in instructional
courses of quantitative analysis; they are used exactly as already
described for Gooch crucibles (Fig. II, 31, 3, a illustrates an excellent
support in a 3-in. funnel) except, of course, that they require no
preparation.
Crucibles fitted with permanent porous plates are cleaned by shaking
out as much of the solid as possible, and then dissolving out the re-
mainder of the solid with a suitable solvent. An alternative method is
to suck watcr or some other liquid through from the reverse side. The
process will be evident upon reference to Fig. II, 33, 2; the crucible is
placed inside the wide glass tube and over the tube leading to the filter-
flask maintained under diminished pressure. Crucibles with permanent
porous plates mp.st not be cleaned by fusion with potassium or sodium
bisulphates; if this procedure is undertaken the crystallisation of the
salt in the pores of the filter disc will crack the crucible on cooling.
* The Worcester Royal Porcelain Co., Ltd., 30, Curzon Street, London, W.l, England.
t Selas Corporation of America, Erie Avenue and D Street, Philadelphia 34, Pa., U.S.A.
Technique of Quantitative Analysis 215
A hot O'lM solution of the tetrasodium salt of ethylenediamine
tetra-acetic acid (see Section III, 148) is an excellent solvent for many
of the precipitates (except Jl1etallic sulphides and ferricyanides)
encountered in analysis. These include barium sulphate, calcium
oxalate, calcium phosphate, calcium oxide, lead carbonate, lead iodate,
lead oxalate, and magnesium ammonium phosphate.
The crucible may either be completely immersed in the
hot reagent or the latter may be drawn by suction
through the crucible.
II, 34. Washing of precipitates.-Most precipitates
are produced in the presence of one or more soluble
compounds. Since the latter are frequently not volatile
at the temperature at which the precipitate is ultimately
dried, it is necessary to wash the precipitate to remove
such material as completely as possible. The minimum
volume of the washing liquid required to remove the ob-
jectionable matter should be used, since no precipitate FIG. II, 33, 2.
is absolutely insoluble. Qualitative tests for the re-
moval of the impurities should be made on small volumes of the filtered
washing solution. Furthermore, it is better to wash with a number of
small portions of the washing liquid, which are well drained between
each washing, than with one or two large portions, or by adding fresh
portions of the washing liquid whilst solution still remains on the filter
(see Section I, 60). The precipitate should never more than one-third
to one-half fill the filter-paper, and the liquid should be kept from
5-10 mm. below the edge.
The ideal washing liquid should comply as far as possible with the
following conditions:
(1) it should have no solvent action upon the precipitate, and
dissolve foreign substances easily;
(2) it should have no dispersive action on the precipitate;
(3) it should form no volatile or insoluble product with the
precipitate;
(4) it should be easily volatile at the temperature of drying of
the precipitate;
(5) it should contain no substance which is likely to interfere
with subsequent determinations in the filtrate.
In general, water should not be used unless it is certain that it will
not dissolve appreciable amounts of the precipitate or peptise it. If
the precipitate is appreciably soluble in water, a common ion is usually
added, since any electrolyte is less soluble in a dilute solution containing
one of its ions than it is in pure water (Section I, 9); as an example the
washing of calcium oxalate with dilute ammonium oxalate solution
may be cited. If the precipitate tends to become colloidal and pass
through the filter-paper (this is frequently observed with gelatinous
or flocculent precipitates), a wash solution containing an electrolyte
must be employed (compare Section I, 56). The nature of the electro-
lyte is immaterial, provided it has no action upon the precipitate during
washing and is volatilised during the final heating. Ammonium salts
are usually selected for this purpose: thus ammonium nitrate solution
is employed for washing ferric hydroxide. In some cases it is possible
to select a solution which will both reduce the solubility of the precipi-
216 Quantitative Inorganic Analysis
tate and prevent peptisation, for example, the use of dilute nitric acid
with silver chloride. Some precipitates tend to oxidise during washing;
in such instances the precipitate cannot be allowed to run dry, and a
special washing solution which re-converts the oxidised compounds
into the original condition must be employed, e.g., acidulated hydrogen
sulphide water for copper sulphide. Gelatinous precipitates, like
aluminium hydroxide,require more washing than crystalline ones,such as
calcium oxalate. With gelatinous precipitates there is also a danger of
channel formation if the wash liquid is allowed to drain completely;
these precipitates should be washed as far as possible by decantation.
The reader may have observed that full details of the technique of
filtration have not so far been given. This is because the filtration
of a precipitate is so closely associated with the washing process that a
consideration of the former is logically deferred until the latter has
been discussed, at least in outline.
II, 35. Technique of filtration.-When the proper filtering medium
(filter-paper, Gooch crucible, etc.) has been prepared, as much as
possible of the supernatant liquid is poured off
t. without disturbing the precipitate by directing the
stream of liquid against a glass rod held against
the lip ofthe beaker (compare Fig. II, 28, 2). The
precautions already mentioned against filling a
filter-paper too full must be taken. In most cases,
particularly if the precipitate settles rapidly or is
gelatinous, washing by decantation may be employed.
Twenty to fifty m!. of a suitable wash liquid is
added to the residue in the beaker, the solid stirred
up and allowed to settle. If the solubility of the
precipitate allows, the solution should be heated,
since, inter alia, the rate of filtration will thus be
increased. When the supernatant liquid is clear, as
much as possible of the clear liquid is decanted
FIG. II, 35, 1. through the filtering medium. This process is
repeated three to five times (or as many times as is
necessary) before the precipitate is transferred to the filter. The
main bulk of the precipitate is first transferred by mixing with the
wash solution and pouring off the suspension, the process being repeated
until most of the solid has been removed from the beaker. The pre-
cipitate adhering to the sides and the bottom of the beaker is removed
as follows. The beaker is grasped in the left hand, and the stirring-rod
is held firmly against the top of the beaker with the index finger and
should project 2-3 cm. beyond the lip; the wash bottle is controlled
by the right hand. The beaker is inclined and a stream of water (or
wash liquid) is directed against the precipitate to dislodge it and wash it
against the rod into the filter. The process is shown diagrammatically
for a filter-paper in Fig. II, 35, 1. For some precipitates, where wash-
ing by decantation is inadmissible because of solubility influences, the
ZI_:kole of the precipitate must be transferred to the filter in this way.
Afte~ ~he above treatment there will generally be small amounts of the
preClpitate adhering to the walls of the beaker. These are removed
by rubbing with a "policeman" (Section II, lOL); when all the par-
ticles have been dislodged, the" policeman" is rinsed with the wash
liquid, and the remaining precipitate transferred to the filter.
Technique of Quantitat'ive Analysis 217
Where the precipitate is washed on the filter, in the last stages the
washing solution is directed along the rim and then gradually towards
the apex of the cone. In all cases, tests for the completeness of washing
must be made by collecting a small sample of the washing solution after
it is estimated that most of the impurities have been removed, and
applying an appropriate qualitative test. Where filtration is carried
out under suction, a small test-tube may be attached to the bottom
of the Gooch funnel by means of a wire ..
II, 36. Drying and ignition of precipitates.-After a precipitate has
been fiftered and washed, it must be brought to a constant composition
before it can be weighed. The further treatment will depend both
upon the nature of the precipitate and upon that of the filtering medium.
This treatment consif';ts in drying or igniting the precipitate. Which
of the latter two terms is employed depends upon the temperature at
which the precipitate is heated. There is, however, no definite tem-
perature below or above which the precipitate is said to be dried or
ignited respectively. The meaning will be adequately conveyed for
our purpose if we designate drying when the temperature is below 250 C.
(the maximum temperature which is readily reached in the usual
thermostatically controlled, electric drying-oven), and ignition above
250 C. up to, say, 1200 C. Precipitates that are to be dried should
be collected on filter-paper, Gooch, sintered glass, or porous porcelain
filter-crucibles. Precipitates that are to be ignited are collected on
filter-paper, porous-porcelain filter-crucibles, Vitreosil filter-crucibles,
or, less commonly, in platinum Gooch or Munroe crucibles. Ignition
is simply effected by placing in a special ignition dish or in a larger
nickel or platinum crucible, as in Fig. II, 31, 4, and heating with the
appropriate burner (Section II, lOA); alternatively, these crucibles
(and, indeed, any type of crucible) may be placed in an electrically
heated muffle furnace, which is equipped with a pyrometer and a means
for controlling the temperature.
Many of the precipitates which are subsequently to be ignited are
filtered through filter-paper, and it is therefore necessary to describe
the method to be adopted in such cases. The exact technique will
depend upon whethel: the precipitate may be safely ignited in contact
with the filter-paper or not. It must be remembered that some
precipitates, such as barium sulphate, may be reduced or changed in
contact with filter-paper or its decomposition products.
A. Incineration of the filter-paper in the presence of the precipitate. On
account of cheapness, porcelain crucibles are usually employed for
this operation, parti()ularly in instructional courses. Silica crucibles,
although somewhat more expensive, are to be preferred because of
their greater resistance to thermal shock. The crucible is first ignited
to constant weight (i.e., to within 00002 g.) at the same temperature
as that to which the precipitate is ultimately heated. The well-
drained filter-paper and precipitate are carefully detached from the
funnel; the filter-paper is folded so as to completely enclose the
precipitate, care being taken not to tear the paper.* The packet is
then placed point down in the weighed crucible, which is supported
on a pipe-clay or, better, a silica triangle resting on a ring stand as in
* For bulky precipitates, such as those containing macerated filter.paper, it is
advisable to remove most of the moisture by a preliminary drying in the steam oven, or
at 100-105 C. .
218 Quantitative Inorganic Analysis
Fig. II, 36, 1. * The crucible is slightly inclined, as shown in the
diagram, and partially covered with the lid, which should rest partly
on the triangle. A very small.flame is then placed under the crucible
lid; drying thus proceeds quickly and without undue risk. When the
moisture has been expelled, the flame is increased slightly so as to
slowly carbonise the paper. The paper should not be allowed to inflame,
as this may cause a mechanical expulsion of fine particles of the pre-
cipitate owing to the rapid escape of the products of combustion; if,
by chance, it does catch fire, the flame should be
extinguished by momentarily placing the cover on
the mouth of the crucible with the aid of a pair of
crucible tongs. When the paper has completely car-
bonised and vapours are no longer evolved, the
flame is moved to the back (bottom) of the crucible
and the carbon slowly burned off whilst the flame
is gradually increased. t After all the carbon has been
burned away, the crucible is covered completely (if
desired, the crucible may be placed in a vertical
position for this purpose) and heated to the required
temperature by means of a Bunsen, Meker, or Fisher
F II 36 1 flame. Usually it takes about 20 minutes to char the
IG. , ,. paper, and 30-60 minutes to complete the ignition.
When the ignition is ended, the flame is removed and, after 1-2
minutes, the crucible and lid are placed in a desiccator containing a
suitable desiccant (Section II, ION), and allowed to cool for 25-30
minutes. The crucible and lid are then weighed. The crucible and
contents are then ignited at the same temperature for 10-20 minutes,
allowed to cool in a desiccator as before, and weighed again. The
ignition is repeated until constant weight is attained. Crucibles should
always be handled with clean crucible tongs.
B. Use of crucible with interior-fitting serrated lid. J. D. Main Smith
(1925) has designed an improved form of crucible lid. This is an
interior-fitting lid of which the vertical flange
is serrated around the edge; it fits into a squat-
shaped crucible, the upper surface of the lid
being about I cm. from the top of the crucible
(Fig. II, 36, 2). The advantages are: (i) gases
or vapours, which are disengaged in the opera-
tion, can escape freely; (ii) loss by creeping,
spattering, and decrepitation are prevented; FIG. II, 36, 2.
(iii) the contents of the crucible can be easily
inspected, since the lid easily swivels up by pressing on one side lightly
with the clean crucible tongs (this is, of course, unnecessary if the
lid is of transparent silica); (iv) liquids can easily be added simply
by pouring on to the lid, the serrations providing ingress into the
crucible. Vitreosil crucibles of 15, 25, 40, and 50 ml. capacity with
serrated lids are commercially available, and are comparatively inex-
pensive. Lids of transparent silica can also be obtained.
* It is preferable to attach the triangle to the ring of a retort stand by bending the
wire ends of the triangle rOlmd it rather than to support it on a tripod. In the former
case, the crucible is more readily accessible and also the height of the crucible above the
burner can be easily adjusted.
t If the carbon on the lid is oxidised only slowly, the cover may be heated separately
in a flame. It is, of course, held in clean crucible tongs.
T echmquf:- VJ 'V .
The ignition of a precipitate in a wet filter-paper is reauh./ _
placing the precipitate and filter-paper into a previously ignited ana
weighed crucible and lid, and conducting the initial heating exactly as
described under A. Care must be taken that a sufficiently large crucible
is used (usually of 40 ml. capacity); an over-large crucible is no dis-
advantage. After the paper has been carbonised and vapours are no
longer evolved, the lid is removed and laid aside upside-down on a clock
glass, and the combustion of the carbon completed at a red heat in the
usual manner. Hthe lid has been blackened by the preliminary heating,
it should be held by the ring upside-down by means of clean crucible
tongs, and carefully ignited over the open crucible by means of a small
flame until all the carbon has been burned off; the clean lid is then
replaced in the crucible, care being taken that any fragments of residue
present fall into the crucible. The crucible and lid are then ignited at
the appropriate temperature to constant weight.
C. Incineration of the filter-paper apart from the precipitate. This
method is employed in all those cases where the ignited substance is
reduced by the burning paper, for example, barium sulphate, lead
sulphate, bismuth oxide, copper oxide, etc. The funnel containing
the precipitate is covered by a piece of qualitative filter-paper upon
which is written the formula of the precipitate and the name of the
owner; the paper is made secure by crumpling its edges over the rim
of the funnel so that they will engage the outer conical portion of the
funnel. The funnel is placed in the steam oven, or in a drying-oven
maintained at 100-105 C., for 1-2 hours or until completely dry. A
sheet of glazed paper about 25 cm. square (white or black, to contrast
with the colour of the precipitate) is placed on the bench away from
all draughts. The dried filter is removed from the funnel, and as much
as possible of the precipitate is removed from the paper and allowed
to drop on a clock glass resting upon the glazed paper. This is readily
done by very gently rubbing the sides of the filter-paper together,
when the bulk of the precipitate becomes detached and drops upon the
clock glass. Any small particles of the precipitate which may have
fallen upon the glazed paper are brushed into the crucible with a small
camel-hair brush. The clock glass containing the precipitate is then
covered with a larger clock glass or with a beaker. The filter-paper is
now carefully folded and placed inside a weighed porcelain or silica
crucible. The crucible is placed on a triangle and the filter-paper
incinerated as detailed in the first paragraph of this Section. The
crucible is allowed to cool, and the filter ash subjected to a suitable
chemical treatment in order to convert any reduced or changed material
into the form finally desired. The cold crucible is then placed upon
the glazed paper and the main part of the precipitate carefully trans-
ferred from the clock glass to the crucible. A small camel-hair brush
will assist in the transfer. Finally, the precipitate is brought to con-
stant weight by heating to the necessary temperature.
Here also the Main Smith crucible may be used. The dried filter-
paper, from which most of the precipitate has been detached as described
above, is first ignited exactly as already detailed. The crucible and
lid are allowed to cool, a small quantity of the liquid chemical required
to convert any reduced or changed material to the form finally desired
is poured on to the lid, and the whole slowly heated to the correct
temperature. The crucible is then allowed to cool, placed upon a
220 Quantitative Inorganic Analysis
sheet of glazed paper, the main part of the precipitate added, and the
whole ignited to constant weight at the appropriate temperature.
II, 37. The care and use of platinum vessels.-Platinum has a very
high melting point (1770 C.). The pure metal is, however, too soft
for general use, and is therefore always hardened with small quantities
of rhodium, iridium, or gold. These alloys are slightly volatile at
temperatures above 1100 0 C., but retain most of the advantageous
properties of pure platinum, such as resistance to most chemical re-
agents, including molten alkali carbonates and hydrofluoric acid (the
exceptions are dealt with below), excellent conductivity of heat, and
extremely small adsorption of water vapour. A 25-ml. platinum
crucible has an area of 80-100 sq. cm. and, in consequence, the error
due to volatility may be appreciable if the crucible is made of an alloy
high in iridium content. The magnitude of this loss will be evident
from the following table, which gives the approximate loss in weight of
crucibles expressed in mg. j 100 sq. cm. jhour at the temperature indicated:
Temp. (0 0.). I Pt~re Pt. 199% Pt - 1 % Jr.! 975% Pt - 25% Jr.
900 000 000 000
1000 008 030 057
1200 081 12 25
Not all crucibles will change in weight (much will depend upon the
exact composition), but this possibility should be borne in mind. If
the financial resources of the laboratory are limited, at least two crucibles
of 25-ml. capacity, provided with covers, should be purchased; these
MISCELLANEOUS OPERATIONS
II, 39. REDUCTION WITH METALS
I
Grams oj Acid,
Pressure (mm. of Per cent HCt in w3ighed in air,
Hg). Acid (vac. wt.). containing 3647 (f.
of Hel.
--
780 20173 180621
770 20197 180407
760 20221 180193
750 20245 179979
740 20269 179766
730 20293 179555
227
_\\
228 . Quantitative Inorganic Analysis
suitable substances are given in Section III, 7. Both methods will be
described. If a solution of an exact normality is required, a solution
of an approximate strength somewhat greater than that desired is
first prepared; this is suitably diluted with water aftcr standardisation
(for a typical calculation, see Section I, 24, Example 15).
The student should read the following theoretical sections before
embarking upon the experimental work:
Sections I, 27-29-theory of acidimetry and alkalimetry;
Section I, 23-equivalent weights, normal solutions.
III, 2. Preparation of constant-boiling-point hydrochloric acid.-
Method A. Mix 500 mi. of pure concentrated hydrochloric acid (sp.
gr. 1'19), preferably of analytical-reagent quality, with 500 ml. of
distilled water; * the resultant acid should have a specific gravity of
110 (test with a hydrometer). Fit up an apparatus consisting of a
15-litre Pyrex distilling-flask surmounted with a splash bulb but no
trap (which might set up a back pressure), and connected to a Liebig's
condenser having a 75-cm. water-jacket and an inner tube of 6-10 mm.
bore. Insert the end of the condenser inside the neck of a Pyrex
Erlenmeyer (conical) flask. Make all connexions with new rubber
stoppers, and arrange that the glass tubing projects at least 2 cm.
beyond the rubber. Place the diluted acid in the flask. To prevent
superheating, allow the flask to rest on a sheet of asbestos in which a
hole is cut for the flame; insulate the upper part of the flask against
heat radiation by means of asbestos paper or cloth. Conduct the
distillation continuously at a rate not exceeding 8-10 ml. per minute.
Do not immerse the condenser in the distillate, but allow the con-
densate to flow freely into the flask. Set aside the first 75 per cent
of the volume of the original distillate for ordinary laboratory use, and
retain the next 10-15 per cent as constant-boiling-point acid. Discard
the residue in the flask (about 100 mI.). Read the barometric pressure
to the nearest mm. at the beginning of the distillation, again after 75
per cent has passed over, and finally at the end ofthe distillation. The
mean of the last two readings is calculated and thc concentration of
the acid interpolated from Table I.
Method B. Mix 400 mi. of pure concentrated hydrochloric acid with
250-400 ml. of distilled water so that the specific gravity of the resul-
tant acid is 110 (test with a hydrometer). Insert a thermometer in
the neck of a I-litre Pyrex distilling-flask so that the bulb is just opposite
the side tube, and attach a Liebig's condenser to the side tube; use
new rubber bungs. Place 500 ml. of the diluted acid in the flask, and
distil the liquid at a rate not exceeding 8-10 ml. per minute (3-4 ml.
per minute is a convenient rate), and collect the distillate in a small
Pyrex flask. From time to time pour off the distillate into a 500-ml.
measuring-cylinder. When 375 ml. has been collected and transferred
to the measuring-cylinder, collect a further 50 ml. in the small Pyrex
flask; watch the thermometer to see that the temperature remains
constant. Remove the receiver and cork it. This contains the pure
constant-boiling-point acid. Note the barometric pressure to the
nearest mm. during the distillation and at the end, and take the
mean value. Interpolate the concentration of the acid from Table I.
* If the concentrated acid has a specific grav~of 1,16, as is often the case, 300 m!.
of water are required for 500 m!. of acid. ~
III, 3. Direct preparation of OlN-hydrochloric acta ll:u .... __
boiling-point acid.-Clean and dry a small, stoppered conical flask; a,
glass-stoppered flask is preferable. After weighing, do not handle the
flask directly with the fingers; handle it with the aid of a strip of
paper or of linen cloth. Add the calculated quantity of constant-
boiling-point acid required for the preparation of 1 litre of OlN-acid
(see Table I) with the aid of a pipette; make the final adjustment
with a small piece of glass capillary, to one end of which a piece of
rubber tubing is attached. By this method it should be possible to
weigh the acid to the nearest centigram. Re-weigh the flask to 0001
g. after replacing the stopper. Add an equal volume of water to
prevent loss of acid, and transfer the contents to a litre volumetric
flask. Wash out the weighing-flask several times with distilled
water and add the washings to the original solution. Make up to the
mark with distilled water. Insert the stopper and mix the solution
thoroughly by shaking and inverting the flask repeatedly.
Note.-Unless a solution of exact normality is required, it is not necessary
to weigh out the exact quantity of constant-boiling acid. The exact
normality may be calculated from the weight of acid used. Thus, if lS305 g.
of acid, prepared at 760 mm., was diluted to 1 litre, its normality would be
lS305/1S0193 = OlOllSN.
Solutions of other concentrations are similarly prepared.
III, 4. Preparation of OlN-hYdrochloric acid and standardisation.-
Measure out by means of a graduated cylinder or a burette 9 ml.
of pure concentrated hydrochloric acid; pour the acid into a litre
volumetric flask or into a litre measuring-cylinder (Fig. II, 24, 1, B)
containing about 500 ml. of distilled water. Make up to the litre
mark with distilled water and thoroughly mix by shaking. This will
give a solution approximately O'lN (1).
Note. 1. If IN-hydrochloric acid is required, use 90 ml. of the concentrated
acid. If OOIN-acid is required, dilute two 50-ml. portions of the approxi-
mately OlN-acid, removed with a 50-ml. pipette, in a volumetric flask to
1 litre.
Approximately O'lN-sulphuric acid is similarly prepared from 3 m!. of
pure concentrated sulphuric acid.
Two excellent methods are available for standardisation. The first
has been widely employed, but the second, of more recent date, is
more convenient, less time-consuming, and equally accurate.
A. Standardisation with anhydrous sodium carbonate. Pure sodium
carbonate. Analytical-reagent-quality * sodium carbonate of 999
per cent purity is obtainable commercially. This contains a little
moisture and must be dehydrated by heating at 260-270 C. for
half an hour and allowed to cool in a desiccator before use. Alterna-
tively, pure sodium carbonate may be prepared by heating A.R.
sodium bicarbonate to 260-270 C. for 60-90 minutes; the tem-
0
perature must not be allowed to exceed 270 C., for above this
temperature the sodium carbonate may lose carbon dioxide. A small
quantity (5-10 g.) of A.R. sodium bicarbonate is placed in a porcelain,
nickel or, best, a platinum crucible, and pressed against the walls of
* Analytical reagent will be abbreviated to A.R.
230 Quantitative Inorganic Analysis
the crucible so as to form a uniformly thick layer. The crucible is
heated by any of the following methods:
(i) Embed the crucible in a sand-bath, immerse the bulb of a 360 C.
thermometer in the sand adjacent to the crucible, and heat the sand-
bath with a free flame; maintain the temperature at 260-270 C. for
one hour.
(ii) Use an air-bath as in Fig. II, 13, 1, or Fig. II, 31, 4.
(iii) Heat in a thermostatically controlled electric oven maintained
at 265 C. (A Pyrex or silica weighing-bottle may also be used.)
It is advisable to stir the mass occasionally. In all cases the crucible
is allowed to cool in a desiccator, and, before it is quite cold, the solid
is transferred to a warm, dry, glass-stoppered tube or bottle, out of
which, when cold, it may be weighed rapidly as required. It is im-
portant to remember that anhydrous sodium carbonate is hygroscopic
and exhibits a tendency to pass into the monohydrate. .
Procedure. Weigh out accurately from a weighing-bottle about 02
g. of the pure sodium carbonate into a 250-ml. conical flask (1), dissolve
it in 50-75 ml. of water, and add 2 drops of methyl orange indicator
(2) or preferably of methyl orange-indigo carmine indicator (Section
I, 29), which gives a very much more satisfactory end point. * Rinse a
clean burette three times with 5-ml. portions of the acid; fill the burette
to a point 2-3 cm. above the zero mark and open the stopcock momen-
tarily in order to fill the jet with liquid. Examine the jet to see that no
air bubbles are enclosed. If there are, more liquid must be run out
until the jet is completely filled. Re-fill, if necessary, to bring the
level above the zero mark; then slowly run out the liquid until
the level is between the 00 and 05-ml. marks. Read the position of the
meniscus to 001 ml. (Section II, 22). Place the conical flask containing
the sodium carbonate solution upon a piece of unglazed white paper
beneath the burette, and run in the acid slowly from the burette.
During the addition of the acid, the flask must be constantly rotated
with one hand whilst the other hand controls the stopcock. Continue
the addition until the methyl orange becomes a very faint yellow or the
green colour commences to become paler, when the methyl orange-
indigo carmine indicator is used. Wash the walls of the flask down with
a little distilled water from a wash bottle, and continue the titration
very carefully by adding the acid dropwise until the colour of the
methyl orange becomes orange or a faint pink, or the colour of the mixed
indicator is a neutral grey; if the end point is overstepped with the
latter indicator, the colour is magenta. This marks the end point of
the titration, and the burette-reading should be taken and recorded in
a note-book. The procedure is repeated with two or three other
portions of sodium carbonate. The first (or preliminary) titration
will indicate the location of the true end point within 05 ml. With
experience and care, subsequent titrations can be carried out very
accurately, and should yield concordant results. From the weights
of sodium carbonate and the volumes of hydrochloric acid employed,
the strength of the acid may be computed for each titration. The
arithmetical mean is taken as the strength of the solution.
FIG. III, 5. 2.
chloride. Allow the barium carbonate to settle, and decant the clear
solution into a litre bottle or flask; dilute to about I litre with carbon
dioxide-free water and shake well. Allow the solution to settle again:
siphon or filter off the solution into a clean bottle fitted with a rubber
stopper. Alternatively, the solution may be stored in an apparatus
similar to that shown in Fig. II, 25, I; a soda-lime guard tube should
be provided.
III,6. Standardisation of the approximately 0-lN-sodium hydroxide.-
If the solution contains carbonate (Procedure A), methyl orange,
methyl orange-indigo carmine, or bromophenol blue must be used in
standardisation against hydrochloric acid of known normality_ Phenol-
phthalein or indicators with a similar pH range, which are affected by
carbon dioxide, cannot be used at the ordinary temperature (compare
Section I, 27). With carbonate-free sodium hydroxide (Procedure B)
phenolphthalein or thymol blue (Section I, 33) may be employed, and
standardisation may be effected against hydrochloric acid, potassium
bi-iodate, potassium hydrogen phthalate, benzoic acid, or other organic
acids (Section III, 7).
Procedure A. With standard hydrochloric acid. Place the OIN
hydrochloric acid, prepared from the constant-boiling-point acid or
which has been standardised by means of sodium carbonate or borax,
in the burette. Transfer 25 ml. of the sodium hydroxide solution into
236 Quantitative Inorganic Analysis
a 250 ml. conical flask with the aid of a pipette (1), dilute with a little
water, add 1-2 drops of methyl orange or 3-4 drops of methyl orange-
indigo carmine indicator, and titrate with the previously standardised
hydrochloric acid. Repeat the titrations until duplicate determinations
agree within 005 ml. of each other.
Note. 1. If another burette is available, the alkali solution may be
placed in it, and definite volumes transferred from the burette to the conical
flask for titrations. This method has the advantage that volumes of the
order of 40 ml. of solution can be conveniently titrated, thus reducing the
experimental error; also, back titration may be effected if the end point is
overstepped.
Calculation of the normality. The normality is readily computed from
the simple relationship:
V A X nA = VB X nB
where VA and nA refer to the volume and known normality of the acid
respectively, VB is the volume of alkali solution required for the
neutralisation, and nB is its (unknown) normality.
Procedure B. With potassium hydrogen phthalate. The A.R. potas-
sium hydrogen phthalate has a purity of at least 999 per cent; it is
almost non-hygroscopic, but, unless a product of guaranteed purity is
0
purchased, it is advisable to dry it at 120 C. for 2 hours, and allow it
to cool in a desiccator. Weigh out three 06-07-g. portions of the salt
into 250-ml. Pyrex or Hysil conical flasks (1), add 75 ml. of boiled-out
water to each portion, stopper each flask and shake gently until the
solid has dissolved. Titrate each solution with the sodium hydroxide
solution contained in a burette, using phenolphthalein or thymol blue
as indicator.
Calculation of normality. This is similar to that described in Section
III, 4. The equivalent weight of potassium hydrogen phthalate is
20422. The mean deviation should not exceed 0,1-0,2 per cent. _
+
HKC sH 40 4 NaOH = NaKCsH404 + H 20
Nob. 1. For elementary students, an approximately O-IN solution is
prepared by weighing out accurately about 5-1 g. of the ordinary A.R.
product, dissolving it in water, and making it up to 250 ml. in a volumetric
flask. Twenty-five-ml. portions are employed in the titrations with the
sodium hydroxide solution. Individual titrations should not differ by more
than 01 ml. The normality is calculated in a similar manner to that given
in Section III, 4; the equivalent weight is 204-22.
III, 7. Other standard substances for acidimetry and alkalimetry.-
In addition to the standard substances already detailed for use in
standardising acids and alkalis, numerous others have been proposed.
A number of these will be briefly described.
A. Sodium oxalate (Na 2C20 4; equiv. wt. = 13402). The A.R.
product has a purity of 999 per cent or better. It is recommended
0
that the salt be dried for 2 hours at 120 C. before use in order to remove
hygroscopic moisture. Upon strong heating the salt largely decom-
poses with the formation of sodium carbonate:
Na 2C20 4 = Na 2C0 3 CO +
If a little carbon dioxide is lost by the decomposition of the sodium
carbonate, no error is introduced because the total alkalinity is un-
affected. Some of the salt (U'"''_'-~ _ ~
weighed into a platinum crucible, which IS LH"
The crucible and lid are heated, while supported in a hOle ~H ~
asbestos, over a small flame for 15-30 minutes until the sodium carbon-
ate formed just begins to fuse. Towards the end of the operation the
lid is moved aside to bring about the complete combustio~ of any
carbon formed. The resultant carbonate is transferred to a conical
flask or beaker, dissolved in water, and titrated with the acid
solution, using methyl orange or methyl orange-indigo carmine as
indicator. The disadvantages of the method are the possibility of
mechanical loss during the evolution of carbon monoxide and its
tedious nature.
B. Mercuric oxide (HgO; equiv. wt. = 10831). Mercuric oxide can
be readily obtained pure and dry, and has a comparatively high equi-
valent weight. It dissolves in potassium bromide solution with the
production of potassium mercuric bromide and an equivalent quantity
of potassium hydroxide:
HgO + 4KBr + H:P = K2[HgBr 4] + 2KOH
A OIN solution of potassium hydroxide is obtained by dissolving
1083 g. of A.R. mercuric oxide in a solution of 200 g. of A.R. potassium
bromide in 300 ml. of water, and diluting to 1 litre. This solution
may be titrated against acids with inter alia phenolphthalein or methyl
orange as indicators.
C. Benzoic acid (HC 7H 5 0 2 ; equiv. wt. = 12212). The A.R. pro-
duct has a purity of at least 999 per cent. For work demanding the
highest accuracy, the acid should' be dried before use by careful fusion
in a platinum crucible at about 130 C., and then powdered in an agate
mortar. Benzoic acid is sparingly soluble in water (which is a dis-
advantage) and must therefore be dissolved in 95 per cent alcohol.
The mode of use is similar to that already described for potassium
hydrogen phthalate (Section III, 6B). For a O'IN solution, of, say,
sodium hydroxide, weigh out accurately 04-g. portions of the acid into
a 250-ml. conical flask, add 10-20 ml. of alcohol, shake until dissolved,
and then titrate the solution with the strong alkali using phenol-
phthalein as indicator. A blank test should be made with the same
volume of alcohol and the indicator: deduct, if necessary, the volume
of the alkali solution consumed in the blank test.
D. Succinic acid (H 2C 4H 4 0 4 ; equiv. wt. = 59045). The A.R.
product or a pure commercial product should be recrystallised from
pure acetone and dried in a vacuum desiccator. The purity is checked
by means of a melting-point determination (185-185'5 C.). The acid
is fairly soluble in water; phenolphthalein is a suitable indicator.
E. Furoic acid (H'C 5H 3 0 3 ; equiv. wt. = 11208). The purified
commercial acid, m.p. 131-132 C., is crystallised once from chloro-
form and dried at 120 C. for 2 hours. The technical product is purified
by one recrystallisation from hot water with the aid of a little animal
charcoal (2. g. of animal charcoal for 20 g. of acid), dried at 120 C.
for 2 hours, and then re-crystallised from chloroform as above. The
resultant solid is pure. The acid is only moderately soluble in cold
water, and is best dissolved in alcohol as detailed under C for benzoic
acid. Phenolphthalein or an indicator of similar pH range must be
used in the titration with a strong base.
~,j~ {Juantztative inorganic Analysis.
F. Adipic acid (H 2'C6 H g 0 4 ; equiv. wt. = 7307). The commercial
acid is crystallised once from hot water with the addition of a little
0
animal charcoal, dried at 120 C. for 2 hours, then recrystallised from
acetone and again dried at 120 C. for 2 hours. The pure acid has a
melting point of 152 C. The acid is slightly soluble in cold water,
but, like furoic acid, it dissolves readily in hot water and can be titrated
in hot solution with an indicator of the phenolphthalein type. It is
best, however, to dissolve it in rectified spirit (compare benzoic acid
above). This is an excellent and inexpensive standard.
G. Potassium bi-iodate (KH(I0 3)2; equiv. wt. = 38995). Unlike
the other solid standards already described, this is a strong acid and
thus permits the use of any indicator having a pH range between 45
and 95 for titration with strong bases (comp'are Section 1,38). It may
be employed for the standardisation of bases which are subsequently
to be used with strong acids; an indicator, such as methyl red, must
then be used. The salt is fairly soluble in water, is anhydrous and
non-hygroscopic, and its aqueous solution is stable for long periods;
the equivalent weight is high. The only disadvantage is that the
pure substance is expensive. A 01N solution of potassium bi-iodate
contains 38995 g. per litre.
Preparation of pure potassium bi-iodate. Dissolve 27 g. of A.R. potassium
iodate in 125 ml. of boiling water, and add a solution of 22 g. of A.R. iodic
acid in 45 ml. of warm water acidified with 6 drops of concentrated hydro-
chloric acid. Potassium bi-iodate separates on cooling. Filter on a sintered-
glass funnel, and wash with cold water. Recrystallise three times from hot
water: use 3 parts of water for 1 part of the salt and stir continuously during
each cooling. Dry the crystals at 100 0 C. for several hours. The purity
exceeds 9995 per cent.
H. Oxalic acid dihydrate (H 2'C20 4,2H 20; equiv. wt. = 63034).
The A.R. acid has been widely used as a standard, but in view of the
possible uncertainty of the water content this is not recommended
except for elementary students. The latter objection may be sur-
mounted if the acid is preserved in a desiccator over deliquescent
sodium bromide.
I. Potassium tetroxalate (KHC204,H2C204,2H20; equiv. wt. =
84'732). This is suitable only for elementary or approximate work
owing to the possible uncertainty of the water content.
J. Potassium bi-tartrate (KHC 4H 40 6 ; equiv. wt. = 18818). The
A.R. product has a purity of 999 per cent. The substance is sparingly
soluble in cold water, and mUiSt be titrated in hot solution, in which it
is more soluble.
Phenolphthalein or thymol blue must be used as indicators for H,
I, and J.
K. Sulphamic acid (NH 2S0 20H; equiv. = 9709). A product of
comparatively high purity is commercially available. It is prepared
by the action of fuming sulphuric acid upon urea:
CO(NH 2)2 +H 2SO 4 + S03 = 2NH 2S0 2 0H + CO 2
Experiment.
c--------
Reading 1.
I Reading 2.
I Difference. __j
1 000 ml. 2610 m!. 2610 ml. (preliminary)
I I
2 000 ml. 2590 m!. 2590 ml.
3 000 m!. 2595 m!. 2595 ml.
In the indirect method, the ammonium salt (other than the carbonate
or bicarbonate) is boiled with a known excess of standard sodium
hydroxide solution. The boiling is continued until no more ammonia
escapes with the steam. The excess of sodium hydroxide is titrated
with standard ac,id, using methyl red (or
methyl orange-indigo carmine) as indicator.
Procedure (direct method). Fit up the
apparatus shown in Fig. III, 18, 1. A is a -D
I-litre Pyrex glass flask provided with a
two-holed rubber stopper which carries a
tap funnel B and a glass spray trap C. The
purpose of the trap is to prevent any drop-
lets of sodium hydroxide solution being
driven over in the subsequent distillation.
D is a Liebig's condenser attached to the JI
trap by means of a rubber bung, and E is
a 350-ml. Pyrex conical flask which serves -
as a receiver. For practice, weigh out 15 g.
of A.R. ammonium chloride or of crude sal
ammoniac, dissolve it in water, and make
up to 250 ml. in a volumetric flask. Shake
thoroughly. Transfer 50 m!. oUhe solution
into the distillation flask and dilute with FIG. III, 18, 1.
200 m!. of water; add a few fragments
of porous porcelain to promote regular ebullition in the subsequent
distillation. Place 100 ml. of standard OIN-hydroch.loric acid in the
receiver .and adjust the flask so that the end of the condenser just dips
into the acid. Make sure that all the corks are fitting tightly. Place
100 ml. of 10 per cent sodium hydroxide solution in the funnel. Run
the sodium hydroxide solution into the flask by opening the tap F;
close the tap as soon as all the alkali has entered. Heat the flask so
that the contents boil gently. Continue the distillation for 30-40
minutes, by ~hich time all the ammonia should have passed over into
the receiver. Open the tap F before removing the flame. Disconnect
the trap from the top of the condenser. Lower the receiver and rinse
the condenser with a little water. Add a few drops of methyl red *
and titrate the excess of acid in the solution with standard O'IN-
sodium hydroxide. Repeat the determination.
Calculate the percentage of NH3 in the solid ammonium salt employed.
Procedure (indirect method). Weigh out accurately 0-1-0-2 g. of
the ammonium salt into a 350-ml. Pyrex or Jena glass conical flask,
* A sharper colour change is obtained with the mixed indicator methyl red-bromo-
cresol green (prepared from 1 part of 02 per cent methyl red in alcohol and 3 parts of
01 per cent bromo-cresol green in alcohol.
248 Quantitative Inorganic Analysis
and add 100 ml. of standard OIN-sodium hydroxide. Place a small
funnel in the neck of the flask in order to prevent mechanical loss, and
boil the mixture until a piece of filter-paper moistened with mercurous
nitrate solution and held in the escaping steam is no longer turned
black. Cool the solution, add a few drops of methyl red, and titrate
with standard OIN-hydrochloric acid. Repeat the determination.
Calculate the percentage of NH3 in the substance.
III,19. Determination of nitrates (sodium nitrate in Chile saltpetre).-
Discussion. Nitrates are reduced to ammonia by means of aluminium,
zinc or, most conveniently, by Devarda's alloy (50Cu, 45Al, 5Zn) i.n
strongly alkaline solution:
3N0 3- + 8Al + 50H- + 2H 0 2 = 8Al0 2 - + 3NHa
The ammonia is distilled into excess of standard acid as in Section
III,18.
Nitrites are similarly reduced, and must be allowed for if nitrate
alone is to be determined.
Procedure. Weigh out accurately about 1 g. of Chile saltpetre.
Dissolve it in water and transfer the solution quantitatively to the
distillation flask of Fig. III, 18, 1. Dilute to about 240 ml. Add 3 g.
of pure, finely divided Devarda's alloy (it should all pass a 20-mesh
sieve). Fit up the apparatus completely (all connexions must be made
with rubber bungs), and place 75-100 ml. of standard 02N-hydrochloric
acid in the receiver (500-ml. Pyrex conical flask). Introduce 10 ml. of
20 per cent sodium hydroxide solution through the funnel, and im-
mediately close the tap. Warm gently to start the reaction, and allow
the apparatus to stand for an hour, by which time the evolution of
hydrogen should have practically ceased and the reduction of nitrate
to ammonia be complete. Then boil the liquid gently and continue the
distillation until 40-50 ml. of liquid remain in the distillation flask.
Open the tap before removing the flame. ,Wash the condenser with a
little distilled water, and titrate the contents of the receiver and the
washings with standard 0'2N-sodium hydroxide, using methyl red
as indicator. Repeat the determination. For very accurate work, it '
is recommended that a blank test be carried out with distilled water.
Calc'ulate the percentage of NaN0 3 in Chile saltpetre.
1 ml. N-HCl == 008501 g. NaNOs
Note. Nitrates can be reduced in neutral solution quantitatively to
ammonia with Arndt's alloy (60 per cent Mg; 40 per cent eu); any siight
spurting of the boiling liquid does not vitiate the titration. Here the
distillation flask will contain 50 mi. of the above nitrate solution, 150 mi.
of water, 2 g. of hydrated magnesium chloride, and 5 g. of the finely divided
alloy. The whole is boiled until about two-thirds of the liquid has passed
over. The distillate is collected in 50 ml. of OIN-hydrochloric acid.
III,20. Determination of nitrogen by Kjeldabl's metbod.-Discussion.
This process is so widely employed in industrial and research laboratories
that an account of it must be included in this book. The principle of
the method is the conversion of the nitrogen of the nitrogenous sub-
stance into ammonia by boiling with concentrated sulphuric acid, which
is fixed by the excess of acid as ammonium sulphate. The latter is
determined by adding an excess of caustic alkali to the solution after
Volumetric Analysis 249
digestion with the acid, and distilling off the liberated ammonia into
standard acid as detailed in Section III, 18. Simple digestion with
concentrated sulphuric acid is, however, a slow process, and various
modifications have been suggested to increase the speed of the reaction.
These include the addition of potassium sulphate, which raises the
boiling point of the acid (Kjeldahl-Gunning process), and of catalysts,
such as mercury, mercuric oxide, anhydrous copper sulphate, selenium,
or a mixture of equal parts of ferrous sulphate and selenium. The
sim pIe process works well for nitrogen determinations in proteins and
also in amines and amides, but is not applicable to nitro, azo, hydrazo,
and cyano compounds without modification. In the presence of
nitrates there is a danger of loss of nitric acid: salicylic acid is then
added ~o the sulphuric acid (proportion: 1 g. to 30 ml.), which fixes
the nitric acid as nitro-salicylic acid. Upon the addition of zinc dust
(1 g.) or of anhydrous sodium thiosulphate (5 g.), the nitro-salicylic
acid is reduced to the amino-compound, which can then be estimated
by the Kjeldahl process.
Procedure. The determination may be carried out with 1'5-2'0 g.
of flour or with acetanilide. Weigh out accurately about 01 g. of
acetanilide into a dry Pyrex Kjeldahl flask-a round-bottomed flask
with a long narrow neck. Add 10 g. of A.R. potassium sulphate,
02 g. of selenium or 05 g. of anhydrous copper sulphate or 05 g. of
equal parts of ferrous sulphate and selenium, and pour 25 ml. of con-
centrated sulphuric acid into the flask in such a way as to wash down
any solid adhering to the neck. Shake until the contents are well
mixed. Support the flask on a hole (45 cm. in diameter) in a piece of
asbestos board, and incline the neck at an angle of about 60. Close
the flask with Eu loosely fitting glass stopper elongated to a point and
having a balloon-shaped top: a small funnel or a flat reagent bottle
stopper will serve the same purpose. Heat the flask in a fume cupboard
with a small flame. When frothing has ceased, increase the flame until
the mixture boils gently. Continue the heating for 30 minutes after
the solution has become colourless or clear (usually 90-120 minutes),
and then allow the solution to cool. When cold, add about 200 ml. of
water carefully and with fr.equent shaking. Transfer completely to
the ammonia-distillation apparatus (Fig. III, 18, 1), add a few frag-
ments of porous porcelain,. followed by excess of sodium hydroxide
solution. Distil off the ammonia into excess of standard acid exactly
as described in Section III, 18. Carry out a blank determination
exactly as above, but with the nitrogen-containing sample omitted,
subtract the" blank," if any.
Calculate the percentage of nitrogen in the solid.
Note. If mercury (07 g.) or mercuric oxide (1 g.) is employed as catalyst,
it is necessary to add 25 ml. of a solution containing 8 g. of sodium thio-
sulphate or 4 g. of potassium sulphide per 100 ml. before distilling in order
to decompose the mercuri-ammonium compounds formed .
.
PRECIPITATION AND COMPLEX-FoRMATION REACTIONS
The procedure has the advantage that the solid is weighed directly
into the reagent, and thus avoids the rapid atmospheric oxidation of the
solution.
Procedure (hyposulphite content of commercial "hydros "). Weigh
out accurately about 04 g. of powdered "hydros" (eodium hypo-
sulphite, usually Na 2S2 0 4,H 2 0) from a stoppered weighing-bottle into a
dry beaker, and cover it with at least a two-fold excess of ammoniacal
silver nitrate solution (prepared by the addition of dilute ammonia
solution in excess of that required to re-dissolve the silver hydroxid~
first formed). As the salt dissolves, it is at once oxidised, and metallic
silver is precipitated. It is essential not to warm the solution. When
dissolution of the salt is complete, filter the precipitated silver on
asbestos in a Gooch crucible (or through a sintered-glass or porous-
porcelain crucible), and wash it with dilute ammonia solution containing
a little ammonium nitrate to prevent peptisation of the finely divided
metal. Transfer the crucible and contents to the beaker in which
precipitation took place, dissolve the metal in nitric acid, and boil thc
solution to remove nitrous fumes. Filter the resultant solution through
a sintered-glass crucible, dilute the filtrate, add 1 ml. of saturated
ferric alum solution, and titrate with standard OIN-thiocyanate.
Calculate the percentage of Na 2S2 0 4 in the sample.
1 ml. N-NH 4CNS (or KCNS) == 008706 g. Na 2S 20 4
III, 37. Determination of cobalt.-Discussion. This method is
based upon the formation of the compound [Co(C sH sN)4](CNS)2
(Sections I, 62K and IV, 330). Excess of a standard solution of
ammonium thiocyanate is added to a solution of the cobaltous salt
containing a little pyridine, the precipitated complex salt is filtered
off, and the excess of thiocyanate titrated with standard silver nitrate
solution.
Procedure. The sample should contain 0,05-0,1 g. of cobalt as
cobaltous salt. Dissolve it in 150 ml. of water in a 250-ml. volumetric
flask, acidify with dilute nitric acid (to litmus), add 3 ml. of pure
pyridine, and excess of standard O'IN -ammonium thiocyanate (1).
The cobalt is precipitated as [Co(C SH 5N)4](CNS)2' which settles readily
and filters easily. Dilute to the mark, and mix thoroughly. Filter a '
portion of the solution through a quantitative filter-paper, and discard
the first few ml. of the filtrate. Transfer 50 ml. of the filtrate to a
beaker or conical flask, dilute to 100 mI., add 1 ml. of concentrated
nitric acid, and then a known excess of standard OIN-silver nitrate.
Add 5 ml. of ferric indicator (2), and titrate the excess of silver nitrate
with O'IN -ammonium thiocyanate in the usual way (Section III, 31).
Calculate the weight of cobalt w from the formula:
w = [ml. of NH 4CNS X N - 5(ml. of AgN0 3 X N)] 002947
* Also called hydrosulphites and dithionites.
Volumetric Analysis ~ol
.
Notes. 1. Standardise the OIN-ammonium thiocyanate against standard
O'lN-silver nitrate: the latter may be standardised, if necessary, against
A.R. sodium chloride.
2. Dissolve 5 g. of A.R. iron alum in a mixture of 40 ml. of water and
10 ml. of 6N-nitric acid.
III, 3S. Determination of nickel.-The procedure is similar to that
given in the preceding Section for Cobalt. The complex has the
formula [Ni(C 5 H 5N)4J(CNS)2 (compare Section IV, 320). The weight
of nickel w is calculated from the formula:
w = [ml. of NH 4CNS X N - 5(ml. of AgN0 3 X N)] 002935
Note. The method may also be applied to the determination of copper
(Section IV, 19E), cadmium (Section IV, 18D), and zinc (Section IV, 34D).
III, 39. Determination of fluoride as lead chlorofluoride.-Discussion.
This method is based upon the precipitation of lead chlorofluoride,
PbCIF, which can be weighed as such, or, more conveniently, the
chlorine is determined by Volhard's method from which the fluorine
content can be calculated. The advantages of the method are: the
precipitate is granular, settles readily, and is easily filtered; the factor
for conversion to fluorine is low; the volumetric procedure is carried
out at pH 3'6-5'6, so that substances which might be co-precipitated,
such as phosphates, sulphates, chromates, and carbonates, do not
interfere. Aluminium must be entirely absent, since even very small
quantities cause low results; a similar effect is produced by boron
(> 005 g.), ammonium (> 05 g.), and sodium or potassium (> 10 g.).
Iron must be removed, but zinc is without effect. Silica does not
vitiate the method, but causes difficulties in filtration.
For practice, the student may determine the percentage of fluorine
in sodium fluoride.
Procedure. Weigh out accurately about 15 g. of dry sodium fluoride,
dissolve it in water, and make up to 250 ml. in a volumetric flask Shake
well. Pipette 25 ml. of the solution into a 400-ml. beaker,* add 2
drops of bromo-phenol blue indicator, 3 ml. of 10 per cent sodium
chloride, and dilute the mixture to 250 ml. Add dilute nitric acid
until the colour just changes to yellow, and then add dilute sodium
hydroxide solution until the colour just changes to blue. Treat with
1 ml. of concentrated hydrochloric acid, then with 50 g. of A.R. lead
nitrate, and heat on the steam-bath. Stir gently until the lead nitrate
has dissolved, and then immediately add 50 g. of crystallised sodium
acetate and stir vigorously. Digest on the steam-bath for 30 minutes,
with occasional stirring, and allow to stand overnight.
Meanwhile, a washing solution of lead chlorofluoride is prepared as
follows. Add a solution of 10 g. of lead nitrate in 200 ml. of water to
100 ml. of a solution containing 10 g. of sodium fluoride and 2 ml. of
concentrated hydrochloric acid, mix it thoroughly, and allow the pre-
cipitate to settle. Decant the supernatant liquid, wash the precipitate
by decantation with 5 portions of water, each of about 200 ml. Finally
add 1 litre of water to the precipitate, shake the mixture at intervals
during an hour, allow the precipitate to settle, and filter the liquid.
Further quantities of wash liquid maybe prepared as needed by treating
* The details apply to a volume of solution corresponding to 001-0[ g. of fluorine.
262 Quantitative Inorganic Analysis
the precipitate with fresh portions of water. The solubility of lead
chlorofiuoride in water is 0325 g. at 25 C.
Separate the original precipitate by decantation through a 'Vhatman
No. 542 or No. 42 paper. Transfer the precipitate to the filter, wash
once with cold water, four or five times with the saturated solution of
lead chlorofluoride, and finally once more with cold water. Transfer
the precipitate and paper to the beaker in which precipitation was made,
stir the paper to a pulp in 100 ml. of 5 per cent nitric acid, and heat on
the steam-bath until the precipitate has dissolved (5 minutes). Add a
slight excess of standard OIN-silver nitrate, digest on the steam-bath
for a further 30 minutes, and allow to cool to room temperature while
protected from the light. Filter the precipitate of silver chloride
through a sintered-glass crucible, wash with a little cold water, and
titrate the residual silver nitrate in the filtrate and washings with
standard OIN-thiocyanate. Subtract the amount of silver found in
the filtrate from that originally added. The difference represents the
amount of silver that was required to combine with the chlorine in the
lead chlorofluoride precipitate.
Calculate the percentage of fluorine in the sample.
1 ml. N-AgN0 3 "" 001900 g. F
III, 40. Determination of arsenic as silver arsenate.- Discussion.
Arsenates in solution are precipitated as silver arsenate, Ag3AsO 4' by
the addition of neutral silver nitrate solution: the solution must be
neutral, or if slightly acid, an excess of sodium acetate must be present
to reduce the acidity; if strongly acid, most of the acid should be
neutralised by aqueous sodium hydroxide. The silver arsenate is
dissolved in dilute nitric acid, and the silver titrated with standard
thiocyanate solution. The silver arsenate has nearly six times the
weight of the arsenic, hence quite small amounts of arsenic may be
determined by this procedure.
Arscnites must first be oxidised by treatment with nitric acid. Small
amounts of antimony and tin do not interfere, but chromates, phos-
phates, molybdates, tungstates, and vanadates, which precipitate as the
silver salts, should be absent. An excessive amount of ammonium
salts has a solvent action on the silver arsenate.
A general method applicable to all arsenic compounds will be de-
scribed.
Procedure. Fuse 05 g. (or less, according to the amount of As
present) of the finely powdered substance with 3-5 g. of a 1 : 1 mixture'
of A.R. sodium carbonate and A.R. potassium nitrate, placing about
one-third of the mixture on top of the charge, or, alternatively, use
ten to twelve times the weight of sodium peroxide. Extract the
cooled melt with hot water, and filter. Acidify the filtrate, containing
the soluble arsenate, with dilute nitric acid, boil to expel carbon
dioxide, and cool. Add sufficient sodium hydroxide solution to give an
alkaline reaction to phenolphthalein, and then discharge the red colour
from the solution by just acidifying with acetic acid. Add a slight
excess of silver nitrate solution with vigorous stirring, and allow the
precipitate to settle in the dark. Pour off the supernatant liquid
through a sintered-glass crucible, wash the precipitate by decantation
with cold distilled water, transfer the precipitate to the crucible, and
wash it free from silver nitrate solution. Wash out the receiver
Volumetric Analysis
thoroughly. Dissolve the silver arsenate in dilute nitric acid (ca.
N) (which leaves any silver chloride undissolved), wash with very dilute
nitric. acid, and make up the filtrate and washings to 250 ml. in a
vol~rrletric flask. Titrate a convenient aliquot portion with standard
ammonium (or potassium) thiocyanate solution in the presence of
ferric alum as indicator (Section III, 31). Calculate the percentage of
arsenic in the sample.
1 ml. N-thiocyanate := 0'02497 g. of As
III, 41. Determination of cyanides.- Discussion. The theory of the
titration of cyanides with silver nitrate solution according to Liebig
(1851) has been given in Section I, 40. All silver salts except the
sulphide are readily soluble in excess of a solution of an alkali cyanide,
hence chloride, bromide, and iodide do not interfere. The only
difficulty in obtaining a sharp end point lies in the fact that silver
cyanide is often precipitated in a curdy form which does not readily
re-dissolve, and, moreover, the end point is not easy to detect with
accuracy.
There are two methods for overcoming these disadvantages. In the
first the precipitation of silver argentocyanide at the end point can be
avoided by the addition of ammonia solution, in which it is readily
soluble;
Ag[Ag(CN)2J + 4NH 4 0H = 2[Ag(NH3hJCN* +
4H 20
If a little potassium iodide solution is added before the titration is
commenced, the sparingly soluble silver iodide, which is insoluble in
ammonia solution, will be precipitated at the end point.
2[Ag(NH3)2JCN + 2KI +
4H 2 0 = 2AgI +
2KCN +
4NH 40H
At the end point, the cyanide, in which silver iodide is soluble, is no
longer present to keep it in solution, and since, unlike the silver argento-
cyanide, it is insoluble in ammonia solution, silver iodide is precipitated.
The precipitation is best seen by viewing against a black background.
In the second method diphenylcarbazide is employed as an adsorption
indicator. The end point is marked by the pink colour becoming
pale violet (almost colourless) on the colloidal precipitate in dilute
solution (ca. 00 IN) before the opalescence is visible. In O'IN solutions,
the colour change is observed on the precipitated particles of silver
argentocyanide.
For practice, the student may determine the percentage of KCN in
potassium cyanide (" single salt ").
NOTE. Potassium cyanide and all other cyanides are deadly poisons, and extreme
care must be taken in their use.
Procedure A. (KeN in potassium cyanide.) Weigh out accurately
about 35 g. of potassium cyanide (single salt) from a glass-stoppered
weighing-bottle, dissolve it in water and make up to 250 ml. in a
volumetric flask. Shake well. Transfer 25 ml. of this solution by
means of a burette and NOT a pipette to a 250-ml. conical flask, add 75
ml. of water, 5-6 ml. of 6N-ammonia solution, and 2 ml. of 10 per cent
potassium iodide solution. Place the flask on a sheet of black paper,
and titrate with standard OIN -silver nitrate. Add the silver- nitrate
solution dropwise as soon as the yellow silver iodide shows any signs
* Or [Ag(NHs)2J+ + [Ag(CN)2J-.
264 Quantitative Inorganic Analysis
of persisting. When 1 drop produces a permanent turbidity, the end
point has been reached. Repeat the titration with two other 25-ml.
portions of the cyanide solution.
Calculate the KCN content of the sample.
1 ml. N-AgNO a == 005204 g. CN == 01304 g. KCN
Procedure B. Transfer 25 ml. of the cyanide solution, prepared as
detailed in Procedure A, by means of a burette and NOT a pipette to a
250-ml. conical flask, add 2 to 3 drops of the diphenylcarbazide indicator,
and titrate against the standard O'IN -silver nitrate until a permanent
violet colour is just produced. Repeat the titration with two other
25-ml. portions of the cyanide solution.
The diphenylcarbazide indicator is prepared by dissolving 01 g. of
diphenylcarbazide in 100 ml. of alcohol.
Calculate the percentage of KCN in the sample.
III, 42. Determination of nickel by potassium cyanide.- Discussion.
This method depends upon the fact that nickel ions can react with
potassium cyanide in slightly ammoniacal solution to form a complex
anion, [Ni(CN)4]-- :
[Ni(NH 3 )6JCl 2 + 4KCN + 6H 0 2 = K 2[Ni(CN)4] + 6NH 40H + 2KCl
If the ammoniacal !Solution of nickel contains a little silver iodide in
suspension and potassium cyanide solution is added, the turbidity will
not disappear until all the nickel has been converted into the complex
cyanide. The slightest excess of cyanide is therefore indicated by the
clearing of the liquid; this excess may be determined exactly by adding
standard silver nitrate solution until the turbidity is reproduced.
AgI +2KCN = K[Ag(CNJ2] KI+
Ag+ + 1- = AgI
Copper, cobalt, &nd zinc, which form complex cytwides, must be
absent; the addition of alkali pyrophosphate, however, renders zinc
harmless. Aluminium, manganese, and iron are kept in solution by
the addition of citri(J acid, tartaric acid, or sodium pyrophosphate.
The potassium cyanide solution is standardised against standard
OIN -silver nitrate as described in Section III, 41. It is evident that:
AgN0 3 == 2KCN == Nij2
i.e., 1 ml. N-AgN0 3 == 01304 g. KCN == 002935 g. Ni
For practice in this determination, the student may determine the
percentage of nickel: (a) in pure nickel ammonium sulphate and (b)
in a steel.
Procedure (Ni in nickel ammonium sulphate). Dissolve 14 g. of A.R.
potassium cyanide in 1 litre of distilled water in a volumetric flask,
and shake well. Prepare a solution of 10 g. of A.R. potassium iodide
in 100 ml. of water. Standardise the potassium cyanide solution
against standard O'IN-silver nitrate (Section 111,41).
Weigh out accurately about 5 g. of pure nickel ammonium sulphate
NiSO 4,(NH4)2S0 4,61I 20, * dissolve it in water containing a little dilute
sulphuric acid, and make up to 250 ml. in a volumetric flask. Shake
* The A.R. product lllay be obtained, e.g., from the Mallinckrodt Chemical ""orks,
70-74 Gold St., New YOl'k 8, N.Y., U.S.A.
Volumetric AnalY8t8
well. Pipette 25 ml. of this solution into a 250-ml. conical flask, add
125 ml. of water, followed by 6N-ammonia solution until the fluid
smells slightly of it, and then add a further 3 ml. If a precipitate
forms, it will re-dissolve if a little ammonium chloride solution is added.
Then add 5 mI. of the potassium iodide solution and a small measured
volume, say 0'5-1 mI., of the standard O'IN-silver nitrate. The silver
iodide produced should cause the liquid to become cloudy. Titrate
with the standard potassium cyanide solution from a burette until the
turbidity just disappears. This will take place when the potassium
cyanide added is equivalent to the nickel in the solution plus the silver
in the known volume (0'5-1 m!.) of silver nitrate solution added.
Add standard O'IN -silver nitrate dropwise from a burette until the
cloudiness due to silver iodide reappears. The excess of potassium
cyanide solution, which is equivalent to the silver nitrate solution, is
thus accurately determined.
Repeat the titration with two other 25-mI. portions of the nickel
solution.
Calculate the volume of the standard potassium cyanide solution
which has reacted with the nickel, and therefrom the percentage of
nickel in the sample.
Procedure (Hi in nickel steel). The m03t accurate method for the
analysis of any steel containing nickel is to precipitate the nickel as
the dimethylglyoxime complex, and to determine the nickel in the
latter.
Weigh out accurately about 1 g. of the nickel steel * into a 350-ml.
conical flask, add 15 ml. of 8N-nitric acid, and place a funnel in the
mouth of the flask to prevent mechanical loss. When the first violent
action is over, boil gently until all the steel has dissolved, adding a little
concentrated hydrochloric acid if necessary. Continue the boiling
for 5 minutes in order to expel oxides of nitrogen. Dilute to 200 mI.,
and add 8 g. of pure tartaric acid. When all the tartaric acid has
dissolved, neutralise with concentrated ammonia solution, and add ca.
1 ml. in excess. If any insoluble material is present, filter it through a
quantitative filter-paper, and wash the latter with hot water. Acidify
0
the solution with hydrochloric acid, heat to 80 C., and add 20-25 ml.
of a 1 per cent alcoholic solution of dimethylglyoxime. Add ammonia
solution until the liquid is slightly alkaline, and allow to stand for 30-
60 minutes, preferably on a water-bath. Filter the precipitate through
a Gooch or Jena sintered-glass crucible, and wash the precipitate
thoroughly with hot water. Dissolve the precipitate in 25 ml. of
6N-nitric acid, add 20 ml. of 9N-sulphuric acid and boil for 20 minutes.
Add 6 g. of citric acid, render the solution slightly ammoniacal, and,
when cold, titrate the nickel as described above.
Calculate the percentage of nickel in the steel.
For another method involving the precipitation of the nickel with
dicyandiamidine sulphate and titration of the precipitated complex
with O'IN -hydrochloric acid, see Section IV, 32D.
III, 43. Determination of thiocyanates.- Discussion. The method
consists in the titration of the thiocyanate in dilute nitric acid solution
with a standard solution of mercuric nitrate, using a little iron alum
* Either Ridsdale's "Nickel steel, No. 22a" (one of the Analysed Samples for
Students) or the Bureau of Analysed Samples "Nickel Steel, No. 222" (a British
Chemical Standard) is suitable.
266 Quantitative Inorganic Analysis
solution as indicator. Immediately the thiocyanate is completely,
converted into the mercuric salt, the solution becomes water-white.
The end point is very sharp.
The method may also be applied to the determination of thiocyanate
and chloride in admixture when the chloride is present in comparatively
small amount (say, 5 per cent of the thiocyanate). The neutral solution
containing the thiocyanate and chloride is treated with excess of
bismuth nitrate solution. The precipitated bismuth oxychloride is
separated, the filtrate acidified with dilute nitric acid, and the thio-
cyanate determined as above. .
Procedure. The following solutions should be prepared:
N-Mercuric nitrate. 1003 Grams of dry A.R. mercury are heated in a
600-ml. beaker (fume cupboard) with 250 ml. of distilled water, and
concentrated nitric acid is added until all the mercury is dissolved. The
action of the acid is rather energetic, especially when hot, and the acid
should be added a little at a time. The solution is boiled to drive off
all nitrous fumes, cooled, transferred to a standardised litre flask, and
diluted to 1000 ml. The O'lN solution is prepared by diluting the N
solution. Since the mercury is pure and can be accurately weighed, i
the solution requires no standardisation.
Mercuric sulphate may replace the nitrate, but offers no advantage;
mercuric chloride cannot be used.
Dilute nitric acid. One hundred and fifty ml. of concentrated nitric
acid are added to 400-500 ml. of distilled water, boiled to drive off
nitrous gases, and diluted to 1000 ml.
Iron alum solution. Twenty-five grams of A.R. iron alum are
dissolved in water, and diluted to 500 ml.
The solution containing about 02 g. of thiocyanate is diluted to
150-200 ml. with distilled water, and 10 ml. of the dilute nitric acid
and 2 ml. of the iron alum solution are added. The solution is titrated
against the standard O'IN-mercuric nitrate solution with constant
agitation until the red colour of the ferric thiocyanate just disappears,
leaving the solution water-white.
1 ml. 0lN-Hg(N0 3)2 "" 0005808 g. CNS
Thiocyanate and chloride in admixture. A solution of bismuth nitrate
is required and is prepared as follows. Ten grams of pure crystallised
bismuth nitrate and 50 ml. of A.R. glacial acetic acid are warmed in a
200-ml. beaker, and 30 ml. of distilled water are added gradually until
complete dissolution has been effected, the solution being stirred
between each addition. When the salt has completely dissolved, the
solution is diluted to 500 ml. with distilled water. Ten m}. of this
solution are required to precipitate approximately 001 g. of chloride,
calculated as sodium chloride.
The neutral solution containing approximately 02 g. of thiocyanate
and 001 g. of chloride (calculated as NaCl) is diluted to 150 ml. with
distilled water, and 10 ml. of the bismuth nitrate solution are added.
The mixture is shaken, left for 10-15 minutes in the cold, filtered
through a quantitative filter-paper, and the precipitate well washed.
The filtrate should give no precipitate upon the addition of a few ml. of
the bismuth nitrate solution. The filtrate is then acidified with dilute
nitric acid, and, after adding 2 ml. of the iron solution, titrated with
OlN-mercuric nitrate solution as above. The chloride may be deter-
Volumetric Analysis 267
mined by any of the usual methods by dissolving the basic chloride on
the filter-paper in dilute nitric acid.
III,44. Determination 01: barium and 01: sulphates.-Barium solutions,
weakly acid with hydrochloric acid, give a red precipitate of barium
" rhodizonate " with a freshly prepared solution of the sodium salt of
rhodizonic acid (dihydroxydiquinoyl, C6 0 4 (OH)2) :
CO CO
OC
/""-C-ONa OC
/""-c-o ..
OC
I /I
C-ONa
+ BaCl 2 I
OC
" ""-Ba + 2N;aCl
C-O/
""-/ ~/
CO CO
The solubility of the red compound is much greater than that of
barium sulphate, hence upon the addition of a sulphate solution to a
solution of a barium salt, the barium will be completely precipitated
when the red colour changes to colourless (in weakly acid solution) or to
yellow (in neutral solution). This forms the basis of a volumetric
method for the determination of barium. To obtain the best results,
it is advisable to work with concentrated solutions (volume up to 10
ml. - O2-05N).
The indicator is freshly prepared as required by dissolving 15 mg. of
sodium "rhodizonate" in 5 Ill!. of water. Ten drops are used for each
titration.
A. Barium. The concentrated solution of the barium salt (5-10 ml.)
is treated with 10 drops of indicator and 1-2 ml. of alcohol. It is then
titrated whilst shaking vigorously with (a) 0'2N-potassium sulphate
(prepared from the A.R. solid) until the colour changes sharply from
red to yellow, or (b) with O2N-sulphuric acid until the colour changes
from red to colourless.
B. Sulphate. Sulphate in acid solution cannot be titrated directly
against a solution of a barium salt, because rhodizonic acid is unstable
and soon decomposes. A known excess of barium chloride solution
(02-05N) is added to the sulphate solution, and the excess of barium
titrated as above. Here also the solutions should be concentrated
(02-05N) and the volume small (10-25 ml.).
Satisfactory results may be obtained as follows. A known volume
of the neutral alkali sulphate solution (say, 10-20 mI.) is placed in a
glass-stoppered conical flask, 1 g. of pure ammonium chloride added,
followed by a known excess of 02N-barium chloride (prepared from
the A.R. salt) and 10 drops of the freshly prepared indicator. The
mixture is thoroughly shaken, and 3 drops of 10 per.cent hydrochloric
acid added; the further addition of one-third the volume of alcohol
improves the end point. The mixture is then titrated with 02N-
potassium sulphate until the colour begins to fade. The alkali sulphate
solution is then added drop wise, with vigorous shaking and waiting for a
short time between the drops, until the red colour has completely dis-
appeared. The titration is repeated until consistent results are obtained.
By subtracting the volume of 02N-potassium sulphate from that
of the 0'2N-barium chloride originally employed, the volume of the
latter equivalent to the sulphate present in the initial solution is found,
since Ba := SO 4'
OXIDATION-REDUCTION TITRATIONS. OXIDIMETRY
AND REDUCTIMETRY
(Section I, 24).
Procedure F. With oxalic acid or potassium tetroxalate. 'Veigh out
accurately either about U g. of A.R. H 2C20 4 ,2H 20 or about 16 g.
of A.R. KHC20.4,H2Cl)f1!rHzO, and make up to 250 ml. in a volumetric
flask. Shake well. Remm-e 25-ml. portions with a pipette, add 150
ml. of ca. 2N-fmlphuric acid, and titrate with the permanganate
solution as detailed under Procedure B (sodium oxalate). Successive
titrations should agree within 01 ml.
Calculation. The partial equation for both reactions is :
+
C20 4- - 2 = 2CO z
hence the equivalent weight of H ZCZ0 4 ,2H zO is 05 mol. or 6303, and
that for KHCz04,H2C204,2HzO is 025 mol. or 6355. Calculate the
normality of the potassium permanganate solution as already detailed.
III, 49. Permanence of potassium permanganate soIutions.-A pure
permanganate solution, provided it is kept free from dust, organic
matter, precipitated manganese dioxide, and reducing vapours, will
keep for a long time. For very accurate work, however, it is advisable
to standardise the solution frequently, preferably with arsenious oxide.
If filtered solutions of permanganate are to be diluted, it is best
to use water which has been re-distilled from alkaline permanganate,
e.g., conductivity water (Section II, 10C). The addition of 10 g. of
potassium hydroxide per litre increases the stability of the solution.
The student is reminded that owing to the decomposition of per-
manganate solution by organic matter of any kind, it cannot be filtered
through filter-paper, nor can it be used in a clip burette, because it is
decomposed by the india-rubber tube. Filtration is carried out
through purified glass wool, asbestos, or a sintered-glass funnel.
276 Q'llantitative Inorganic Analysis
282 Quantitative Inorganic Analysis
mality; this gives the volume of N solution to which it is equivalent.
If the latter volume is multiplied by the milli-equivalent of iron (0'05584
g.), the weight of iron in the volume of solution titrated is obtained,
from which the percentage of iron is readily calculated.
III, 53. Determination of the total iron in an iron ore.-For practice,
the student may employ either spathic iron ore (largely ferrous carbon-
ate)* or the iron ore supplied by the instructor. Weigh out accurately
about 2 g. of the finely ground ore and dissolve it in 100 ml. of dilute
hydrochloric acid (1 : 1) in a conical flask carrying a short funnel in the
neck. Warm gently, and continue the heating until the residue is free
from coloured material. Rinse down the funnel and the neck of the
flask with distilled water, cool, and filter the liquid through a hardened
quantitative filter-paper into a 250-ml. volumetric flask. Wash with
very dilute hydrochloric acid and allow the washings to pass into the
flask. Remove the funnel and make up to the mark. Shake well.
Remove 50 ml. of the liquid by means of a pipette to a conical flask,
heat to boiling, and reduce the ferric salt by the stannous chloride method
(Section III, 51A). Pour the reduced solution into 400 ml. of water
containing 25 ml. of the Zimmermann-Rcinhardt solution (Section
III, 46), and titrate slowly with standard O'lN-potassium perman-
ganate to the first pink colour which is stable for 15 seconds. Repeat
the titration with two other 50-ml. portions of iron in the iron ore.
.
=====~ III, 54. Determination of calcium in calcium carbonate.- Discussion.
Metals, such as calcium, copper, lead, and zinc, which give slightly
soluble oxalates may be determined by dissolving the washed precipitate
in dilute sulphuric acid and titrating with standard permanganate
solution. The method is widely used for the estimation of calcium.
The calcium is precipitated as the oxalate by the addition of ammonium
oxalate solution to a dilute hydrochloric acid solution of the element,
followed by neutralisation of the acid with dilute ammonia solution.
The washed precipitate is dissolved in dilute sulphuric acid, and the
liberated oxalic acid titrated with standard permanganate solution.
CaC 20 4 +
H 2SO 4 = CaSO 4 H ZC2 0 4 +
2KMnO 4 + 3H zSO 4 + 5H 2C2 0 4
+
= KzSO 4 2MnSO 4 10C0 2 + + 8H 0 2
It must be pointed out that the above method is not quite satisfactory
for the determination of lead, because of the formation of a coating of
lead sulphate over the lead oxalate. In this case the following pro-
cedure, which can be applied to all the elements given above, should
be used. The oxalate of the metal is precipitated by a known excess
of oxalic acid or ammonium oxalate solution in the presence of ammonia
solution (details are given below), the precipitate is filtered and well
washed, and the excess of oxalate in the filtrate and washings deter-
mined by titration with standard potassium permanganate solution
in the usual manner.
Procedure. ,Veigh out accurately 015-02 g. of calcium carbonate,
preferably of A.R. grade, into a 400-ml. beaker. Add 20 ml. of water
and cover the beaker with a clock glass. Add 10 ml. of dilute hydro-
chloric acid (1 : 1) and warm until the solid has dissolved. Rinse the
* Suitable iron ores are Ridsdale's " Iron Ore, No. 17 " (one of the Analysed Samples
for Students) and" Iron Ore' A ' " (a British Chemical Standard) of the Bureau of
Analysed Samples.
Volumetric Analysis 283
sides of the vessel and the clock glass, dilute to 200 mI., and add a few
drops of methyl red indicator. Heat the solution to boiling, and add
a clear solution of 15 g. of ammonium oxalate dissolved in 25 mi. of
water slowly and with constant stirring; some calcium oxalate may
be precipitated in the acid solution owing to the large excess used.
To the hot solution (70-80 C.) add dilute ammonia solution (1 : 1)
dtopwise and with stirring from a burette until the liquid is neutral or
faintly alkaline (colour change from red to yellow). Allow the solution
to stand for an hour in a warm place. Decant the clear supernatant
liquid through a What man No. 40 or No. 540 filter-paper; test t,h(~
filtrate for the presence of calcium with ammonium oxalate. Transfer
the precipitate quantitatively to the filter (Section II, 28), and wash
the precipitate on the filter repeatedly with small quantities of cold
water until the washings are oxalate- and chloride-free. Pierce a hole
in the filter with a pointed glass rod, and wash the bulk of the precipitate
through the funnel into a conical flask with hot water. Treat the
filter with small quantities of dilute sulphuric acid (1 : 8), and again
wash .into the flask. Finally wash the filter-paper thoroughly with
hot water. When the precipitate has completely dissolved (add more
dilute sulphuric acid, if necessary), dilute the solution to about 200 mi.,
and titrate with standard O'lN -potassium permanganate (for details,
seEf Section III, 48, Procedure B).
The calcium oxalate precipitate may also be filtered through a
sintered-glass or .porous-porcelain crucible. The precipitate is then
washed with dilute sulphuric acid (5 per cent) until dissolved. The
sulphuric acid is added in small portions, and is allowed to remain in
contact with the precipitate before being drawn into the suction flask.
The solution in the flask is diluted and titrated with standard O'lN-
permanganate.
Repeat the determination with two other samples of the calcium
carbonate.
Calculate t"!:e percentage of calcium in the calcium carbonate.
1 ml. N-K~n04 == 002004 g. Ca == 002804 g. CaO
III, 55. Analysis of hydrogen peroxide.-Discussion. Hydrogen
peroxide is marketed in four concentrations, "10-," "20-," "40-,"
and" 100-volume "concentrations. The" lO-volume " solution refers
to the fact that the solution, when fully decomposed by heat, yields
10 times its volume of oxygen measured at 0 C. and 760 mm.
2H 2 0 2 = 2H 2 0 +O 2
2 X 3402 g. . 224litres (at N.T.P.)
Upon leaching the melt with water, the sodium chromate dissolves and
the iron is precipitated as ferric hydroxide:
NaFe0 2 + 2H 0 2 = NaOH +
Fe(OH)3
2NazO + 2H 0 2 = 4NaOH
The excess of peroxide is decomposed by boiling the alkaline solution.
The precipitate is filtered off after diluting the solution; the filtrate
is acidified with hydrochloric acid, a known volume of excess of ferrous
298 Quantitative Inorganic Analysis
ammonium sulphate solution is added, and the excess of ferrous salt is
titrated with standard potassium dichromate solution.
2Na2Cr0 4 + 2HCl = Na 2Cr20 7 + 2NaCl +
H 20
Na2Cr207 + 6FeS0 4 + 14HCI
= 2CrC1 2 + 2N aCl + 2Fe 2 (SO 4h +2FeCI a +7H 20
Procedure. Weigh out accurately about 05 g. of the very finely
powdered are * into a 30-35-ml. nickel, or heavy-walled porcelain,
crucible, add 4 g. of sodium peroxide, and mix thoroughly by means of
a thin glass rod. Remove any powder adhering to the rod by stirring
about 1 g. of sodium peroxide with it; cover the mixture in the crucible
with this peroxide. Place the lid on the crucible, and gently heat the
covered crucible in the fume cupboard over a small flame until the
mass is quite liquid (about 10 minutes); keep fused for a further 10
minutes at a dull red heat. Allow to cool, and when a solid crust has
formed, add 4 g. more of the sodium peroxide, and fuse the mixture
again at a cherry-red heat for 10 minutes. Allow the crucible to cool
and place it in a 60-ml. Pyrex beaker containing a little distilled water.
Cover the beaker with a clock glass (or with a Fisher" speedyvap "
beaker cover), add a little warm water, and, after the violent action has
subsided, remove the crucible and wash it thoroughly, collecting the
washings in the same beaker. Boil the liquid for 30 minutes, keeping
the beaker covered (this decomposes the hydrogen peroxide), add 250
ml. of boiling water, and allow the precipitate to settle. Filter through
a hardened 15-cm. filter-paper or, better, through a sintered-glass
crucible,t and wash the residue thoroughly with boiling water until free
from chromate. (The residue should be completely soluble in concen-
trated hydrochloric acid; no black gritty particles should remain.
If this is not the case, decomposition is not complete, and the determina-
tion must be started afresh.) Evaporate the filtrate to about 200 mI.,
cool, and add 9N -sulphuric acid cautiously until acid. Cool, transfer
to a 250-ml. measuring-flask, and make up to the mark with distilled
water. Shake well. Remove 50 ml. of this solution with a pipette,
add 50 m!. of O'IN -ferrous ammonium sulphate (Section III, 48,
Procedure E), 200 ml. of 2N-sulphuric acid, and 05 ml. of N-phenyl-
anthranilic acid indicator. Titrate with standard O'IN-potassium
dichromate until the colour changes from green to violet-red. Alterna-
tively, take 50 m!. of the solution, add 50 ml. of OIN -ferrous ammonium
sulphate, 5 ml. of syrupy phosphoric acid, and 04 ml. of sodium di-
phenylamine sulphonate indicator; dilute to 200 mI., and titrate with
standard OIN-potassium dichromate until the green colour changes
to violet-blue. Repeat until two titrations agree within 01 ml.
The ferrous ammonium sulphate solution must be standardised by
titration with the O'IN -potassium dichromate; the same indicator as
was employed in the above determination must be used.
Calculate the volume of the ferrous solution which was oxidised by
the dichromate originating from the chromite, and from this the per-
centage of chromium in the original ore.
1 ml. N-Fe++ "" 1 ml. N-K 2Cr 20 7 '=' 002534 g. Cr 20 a "" 001734 g. Cr
* Ridsdale's" Chrome Iron Ore, No. 49G" (one of the Analysed Samples for Students)
is suitable for this determination.
t If the latter is used, it is unnecessary to add more than 150 m!. of boiling water'
the subsequent concentration is then avoided. '
Volumetric Analysis 299
III, 72. Determination of manganese in steel or in manganese ore.
(Pattinson's method).-Discu8sion. When a solut~on containing iron,
zinc, and manganese salts is treated with bromine water and calcium
carbonate, all the manganese is precipitated in the quadriva,lent condi-
tion as the manganite (e.g., ZnO,Mn0 2). The precipitate is dissolved
in excess of ferrous solution, and the excess of the latter titrated with
standard potassium dichromate solution.
Mn02 + 2FeS0 4 + 2H 2S0 4 = Fe 2 (S04h + MnS0 4 + 2H 0 2
N. H 2 SO 4 , HNO a HCI0 4
1 144 161 170
2 144 162 171
4 143 161 175
6 - - 182
8 142 156 187
I
300
Vol1lmetric Analysis 301
Since the single electrode potential varies considerably with the anion of
the acid used, but only slightly with its concentration, these authors conclude
that the results support the view that the following equilibria are present in
the three solutions respectively:
[Ce(S04)4 ----] [Ce(N0 3)6--]
[Ce++ H ] X [S04 ]4 [Ce HH ] X [N0 3 ]6
OlN arsenious oxide solution, and titrate 25 ml. of this WICH __~
solution as described above. Full details for the preparation of the solution
and the method for the calculation of the result will be found in Sectionm.
48, Proceiiure A, Note 1.
Procedure B. Standardisation against pure iron. Weigh out accurately
015-020 g. of A.R. iron wire, and then proceed exactly as described
in Section III, 48, Procedure O. Titrate the resulting ferrous solution
with tre ceric sulphate solution, using any of the indicators referred
to in the Discussion.
Another method, which incidentally utilises the stannous chloride
process of reduction, is the following. Weigh out accurately about
020 g. of A.R. iron wire into a 400-mL beaker or into a 350-mL conical
flask. Add 5 mI. of water and 10 mL of concentrated hydrochloric
acid. Warm the solution until all the iron has dissolved. Heat the
solution to boiling, an~ add freshly prepared 05N-stannous chloride,
dropwise and with c-onstant stirring, from a burette or separating-
funnel (Section III, 51A) until the hot solution nO longer shows any
yellow colour and a few drops of the reducing agent causes the colour
to change from yellow to very pa,le green. Cool, add 5 mL of concen-
trated hydrochloric acid, dilute the- solution with cold air-free water to
250 mI., and add 10 mL of a saturated solution of mercuric chloride.
A slight white silky precipitate of mercutous chloride should be formed,
sometimes after 1-2 minutes. (If the precipitate is bulky or grey in
colour, the solution should be rejected, and the estimation repeated.)
Add a drop or two of ferroin (or 05 mL of N-phenylanthranilic acid)
and titrate slowly with the ceric sulphate solution until the sharp colour
change from red to a faint yellow or green colour occurs. Alternatively,
add 5 mL of syrupy phosphoric acid, 05 mL of sodium diphenylamine
sulphonate, then titrate the mixture with the ceric sulphate solution
(proceed slowly near the end point) until the solution assumes a distinct
purple tint. Repeat with two other samples of the A.R. iron wire.
Calculate the normality of the ceric sulphate solution.
Procedure O. Standardisation against ferrous ammonium sulphate.
As pointed out in Section III, 46, this method is only suitable for work
requiring moderate accuracy or for elementary students. Prepare an
approximately OlN -solution of ferrous ammonium sulphate (Section
III, 48, Procedure E). Transfer 25 mL of this solution to a conical flask,
add 25 mL of N-sulphuric acid, and the appropriate quantity of erio-
glaucine, ferroin, or N-phenylanthranilic acid (see Discussion above);
titrate with the ceric sulphate solution to the first sharp colour change.
Carry out two or at most three tit rations ; these should agree within
01 mL
Alternatively, the ferrous solution may be placed in the burette,
and 25-mL portions of the ceric solution titrated. The end points are
equally satisfactory, although when once the colour of the ceric solution
has been bleached, it is advisable to add the ferrous solution slowly.
Calculate the normality of the ceric sulphate solution.
Procedure D. Standardisation against anhydrous potassium ferrocyanide.
Dehydrate about 50 g. of A.R. potassium ferrocyanide trihydrate
by heating the powdered solid to constant weight at 100-110 C.,
and allow to cool in a desiccator over anhydrous calcium chloride.
Prepare a OlN solution by weighing out 18415 g. of the anhydrous
;jUO ctuantitative Inorganic Analysis
salt and dissolving it in 500 m!. of boiled-out water in a volumetric
flask (I).
Dilute 25 m!. of the ferrocyanide solution with 25 ml. of water, add
50 m!. of 4N-sulphuric acid, and either 05 ml. of N-phenylanthranilic
acid or 05 m!. of erioglaucine indicator, and titrate with the eerie -
sulphate solution to the first sharp colour change. Repeat the titration
with two other 25-ml. portions of the ferrocyanide solution; these
should give titres of eerie sulphate solution which agree well within
01 ml. Calculate the normality of the eerie sulphate solution. ,
Alternatively, weigh out accurately about 095 g. of the anhydrous
potassium ferro cyanide into a 350-m). conical flask or 400-ml. beaker,
dissolve it in 100 ml. of 2N-sulphuric acid, add N-phenylanthranilic
acid or erioglaucine indicator, and titrate with the eerie sulphate
solution until the first sharp colour change occurs. Repeat with two
other samples of approximately equal weight of anhydrous potassium
ferrocyanide. Calculate the normality of the eerie sulphate solution.
Note. I. The molecular weight and the equivalent weight of anhydrous
potassium ferrocyanide is 36834. The aqueous solution is stable for several
days. A solution of potassium ferrocyanide in 2N-sulphuric acid is un-
stable; it soon develops a bluish-green coloration, and should therefore be
titrated within an hour of its preparation.
Procedure E. standardisation against anhydrous sodium thiosulphate.
Weigh out accurately about 04 g. (I) of anhydrous sodium thiosulphate
(Section III, 101) into a 500-m!. conical flask, dissolve it in water, add
03-04 g. of A.R. potassium iodide, 20 ml. of 02 per cent starch
solution, dilute to 250 ml., and titrate with the eerie sulphate solution
to the starch-iodine end point. Repeat the titration with two other
similar portions of anhydrous sodium thiosulphate. Calculate' the
normality of the eerie sulphate solution.
Note. 1. Alternatively, a O'IN solution of sodium thiosulphate may be
prepared by weighing out 3953 g. of anhydrous sodium thiosulphate (the
equivalent and molecular weight is 15813) and dissolving it in 250 ml. of
boiled-out distilled water in a volumetric flask. Twenty-five-ml. portions
are titrated as detailed above. The normality of the eerie sulphate solution
is then calculated (see Section m, 4A).
...
REDUCTIONS WITH TITANOUS SALTS
111,86. General discussion.-E. Knecht (1903) first suggested the use
of titanous chloride for the determination of iron. This determination
differs from those already described in that the iron is reduced instead
of oxidised, for example:
FeCl 3 + TiCl 3 = FeCl 2 + TiCl 4
The end point of the reaction is judged by the use of an indicator such
as methylene blue, which is reduced and decolorised when the titanous
solution is present in slight excess, or of ammonium thiocyanate,
which remains red as long as any ferric salt is present. The latter is
generally preferred, because methylene blue is somewhat slow in
reaction below about 35 C.; if, however, one drop of 10 per cent sodium
salicylate solution is added, the change is in~tantaneous at the ordinary
temperature.
Titanous chloride is a more powerful reducing agent thim stannous
chloride (compare Table XVI in Chapter I). It is oxidised rapidly in the
air, and should be kept out of direct sunlight. A. S. Russell (1926) has
shown that titanous sulphate in 4N-sulphuric acid solution is more stable
to air than is the chloride (compare ferrous chloride and ferrous sulphate),
and, indeed, its titre against potassium permanganate solution when
kept in a burette exposed to air remains unchanged for 12 hours.
Nevertheless, for accurate analysis and for work requiring a large
number of routine determinations, solutions of both titanous chloride
and sulphate should be stored in an atmosphere of hydrogen; titrations,
particularly of the chloride, are best carried out in an atmosphere of
carbon dioxide.
Formerly titanous salts were employed for numerous quantitative
estimations; * many of these determinations can now be made more
simply by other methods. The chief present uses of the reagent are in
the analysis of ferric salts, of organic nitro and nitroso-compounds,
azo dyes, and various routine analyses. Only the first-named falls
within the com pass of this volume. The reaction with a nitro-com pound
may be written:
RN0 2 + 6Ti+++ + 6H+ = R'NH z + 6Ti++++ + 2H 0 2
hence NO z == 6Ti+++ t
III, 87. Preparation of titanous solutions.-A. Titanous chloride
solution. Boil 60 ml. of commercial titanous chloride solution (15--20
per cent TiCl a) for 1 minute with 100 ml. of concentrated hydrochloric
* For complete details, see E. Knecht and E. Hibbert, New Reduction Methods of
Volumetric Analysis, 1925 (Longmans, Green and Co.), W. M. Thornton, Titanium,
1927 (Chemical Catalog Co.).
t For further details, see J. F. Thorpe and 1\1. A. 'Nhiteley, A Student's Manual of
Volumetric Analysis, 1925 (Longmans, Green and Co.); W. l\L Cumming, I. V. Hopper,
and T. S. '\Theeler, Systematic Organic Ohemistry, New Edition, 1950 (Constable and Co.);
and S. Siggia, Quantitative Organic Analysis via Functional Groups, 1949 (J. Wiley:
Chapman and Hall).
314
Volumetric Analysis 315
acid * in a small flask, allow to cool in an atmosphere of nitrogen, and
make up to about 2 litres with boiled-out water in the storage bottle
(Fig. 11, 25, 1). The solution should be thoroughly mixed by shaking
and, when freshly prepared, should fill the bottle to the neck; other-
wise air remains, which must be completely displaced by hydrogen.
The burette is first completely filled with the solution. The storage
bottle, etc., is connected to a Kipp's apparatus generating hydrogen.
The tap of the burette is opened so that the latter is emptied, and
hydrogen is passed through the system in order to displace the residual
air. The tap is now closed, and the burette filled with the solution by
suitably rotating the tap. It is now ready for standardisation and for
use.
B. Titanous sulphate solution. This is similarly prepared by boiling 60
ml. of commercial titanous sulphate solution (15-20 per cent Ti 2 (SO 4h)
for 2-3 minutes with 200 ml. of 1 : 3 sulphuric acid in a small flask,
allowing to cool, ancrdiluting exactly as detailed under titanous chloride. t
If 3-4N -sulphuric acid is used for dilution, the stability of the solution
is considerably increased. Another method is to reduce a solution of
titanic sulphate in 4N -sulphuric acid with liquid zinc amalgam (Section
III, 95) for 1-2 minutes, and then to decant the resultant titanous
sulphate solution into a storage vessel or flask. This method is par-
ticularly valuable when relatively small volumes of the solution are
required.
III, 88. Standardisation of the titanous sulphate (or titanous chloride)
solution.-A. With pure iron. Weigh out accurately 1001 g. of A.R.
iron wire (assay value 999 per cent; see Section III, 46) into a long-
necked flask held in an inclined position, or into a conical flask carrying
a short funnel in the mouth, and add about 100 ml. of 5N-sulphuric acid.
When all the iron has passed into solution, transfer quantitatively to a
500-ml. volume~ric flask, add a further 200 ml. of 5N-sulphuric acid,
and make up to the mark. Shake thoroughly. Pipette 25 ml. of this
solution (== 00500 g. Fe) into a 250-350-ml. conical flask, fitted with a
three-holed rubber stopper carrying tubes as described in Section III, .
116B), and carefully oxidise with potassium permanganate solution
of about 0'02N strength until a faint pink tinge is obtained. Boil
vigorously to expel dissolved oxygen whilst a slow current of carbon
dioxide is passed through the flask. Cool the solution, add 10-20 ml.
of 10 per cent ammonium or potassium thiocyanate solution and run
in the titanous sulphate (or chloride) solution until the red colour, due
to "ferric thiocyanate," has disappeared. The stream of carbon
dioxide is maintained throughout the whole of the operation. The
reduction of the last few mg. of the ferric salt is somewhat slow, and it
is therefore best to add the titanous solution dropwise with intervals
of several seconds between the drops when the end point has almost
been reached. The use of a large excess of thiocyanate renders the
end point much sharper. It is immaterial whether the iron is present
in sulphuric or hydrochloric acid solution, but the presence of some
mineral acid is essential, as otherwise the indicator is not sensitive.
* Commercial titanous chloride solution sometimes contains sulphides, which are
eliminated as hydrogen sulphide on boiling. .
t A more concentrated solution of titanous sulphate is generally used for the titration
of nitro and other organic compounds. It is prepared by boiling 300 m!. of commercial
titanous sulphate solution (15-20 per cent) with 500 m!. of 1 : 3 sulphuric acid for It few
minutes, cooling, and making up to 1 litre. .
316 Quantitative Inorganic Analysis
Repeat the titration with two other 25-ml. portions of the iron
solution.
Calculate the weight of iron equivalent to 1 ml. of the titanous
solution.
B. With ferrous ammonium sulphate. 'Weigh out accurately 3511 g.
of A.R. ferrous ammonium sulphate (Section 111,46), dissolve it in water,
add about 150 ml. of 5N-sulphuric acid, and make up the solution to
250 ml. in a standard flask. Shake thoroughly. Pipette 25 m!. of this
solution ("" 00500 g. of Fe) into a 250-350-ml. conical flask and proceed
as described under A. This method is less accurate than that employ-
ing pure iron (for reasons, see Sections III, 46, and III, 48, Procedure E).
A.R. ferric ammonium sulphate (iron alum) may also be used for the
standardisation.
111,89. Determination of iron in an ore.-Weigh out accurately about
2 g. of the iron ore,* dissolve it in 100 ml. of 1 : I-hydrochloric acid,
and make up the solution to 250 ml. in a volumetric flask as described
in Section III, 53. Pipette 25 ml. of this solution into a 250-m!.
conical flask, and precipitate the iron by the addition of ammonium
hydroxide solution. Oxidise the ferrous hydroxide by adding excess
of pure hydrogen peroxide solution. Boil for 10 minutes to decompose
the excess of hydrogen peroxide. Cool, add concentrated hydrochloric
acid until the acid content of the solution is about 10 per cent by volume,
then 10 ml. of 10 per cent ammonium thiocyanate solution. Titrate
with the standardised titanous sulphate (or chloride) solution in an
atmosphere of carbon dioxide until the red colour just disappears
(Section III, 88A). Repeat with two other 25-ml. portions of the
solution.
From the results, calculate the percentage of total iron in the sample
of ore used.
* Ridsdale's " Iron Ore, No. 17 " (one of the Analysed Samples for Students) or the
Bureau of Analysed Samples" Iron Ore' A ' " (one of the British Chemical Standards)
may be used.
REDUCTIONS WITH AMALGAMATED ZINC AND WITH
LIQUID AMALGAMS
H 20 2 + 2H+ + 21- = 2H 20 + 12
Br0 3- + 6H+ + 61- = Br- + 31 + 3H 20 2
10 3- + 6H+ + 51- = 31 + 3H 0 2 2
* For example, by Merck and Co. Inc., Rahway, N.J., U.S.A., by Mallinckrodt
Chemical \Vorks, 70-74 Gold Street, New York, N.Y., and by J. T. Baker Chemical Co.,
Phillipsburg, N.J., U.S.A.
t See, for example, Fig. II, 5, 3, in the author's Text Book of Practical Organic
Chemistry, Second Edition, 1951 (Longmans, Green and Co.).
Volumetric Analysis 335
Its equivalent weight as an oxidising agent is i mol. or 214'02/6; a
OIN solution therefore contains 3567 g. of potassium iodate per litre.
Weigh out accurately 014-015 g. of pure dry potassium iodate,
dissolve it in 25 m!. of cold, boiled-out distilled water, add 2 g. of
iodate-free potassium iodide * and 5 ml. of 2N-sulphuric acid (1).
Titrate the liberated iodine with the thiosulphate solution with
constant stirring. When the colour of the liquid has become a pale
yellow, dilute to ca. 200 ml. with distilled water, add 2 m!. of starch
solution, and continue the titration until the colour changes from blue
to colourless. Repeat with two other similar portions of potassium
iodate.
Calculate the normality of the sodium thiosulphate solution.
- 1 illl. N-Na 2S:;iOs == 003567 g. K10 a
Note. 1. Potassium iodate has a small equivalent weight (3567) so that
the error in weighing 014-0-15 g. may be appreciable. In this case it is
better to weigh Qut accurately 3567 g. of the A.R. salt (if a slightly different
weight is used, the exact normality is calculated), dissolve it in water, and
make up to 1 litre in a volumetric flask. Twenty-five m!. of this solution
are treated with excess of pure potassium iodide (1 g. of the solid or 10 m!.
of 10 per cent solution), followed by 3 ml. of 2N-sulphuric acid, and the
liberated iodine is titrated as detailed above. The titrations are repeated
until two agree within 01 ml.; not more than three titrations should be
necessary. The normality of the sodium thiosulphate solution is then
calculated (see Section m, 4A).
B. With potassium bromate. Potassium bromate is very similar in
properties to potassium iodate; its only advantage over the latter is
that it is less expensive. A.R. potassium bromate has a purity of at
least 999 per cent. It may be dried at 120-150 C., and its aqueous
solution is stable. The substance reacts with potassium iodide in acid
solution in accordance with the equation:
KBr0 3 + 6KI + 6HCl = KBr + 6KCl + 31 + 3H 0 2 2
2Cu++ + 41- ~ Cu I + 12
2 2
essential to be certain that all the chlorine reacts with the potassium
iodide solution. With pyrolusite, the following reactions occur :
+
Mn0 2 4HCl = MnC1 2 2H 20 + +
C1 2
2KI + C1 2 = 2KCl +
I2
Procedure. A distillation apparatus, such as is portrayed dia-
grammatically in Fig. III, 107, 1 or Fig. III, 107, 2, is employed. The
apparatus fitted with ground-glass joints is to be preferred, since
chlorine attacks rubber.
The apparatus in Fig. III, 107, 1, consists of a distillation flask of
about 200 ml. capacity, connected to two U (Peligot) tubes containing
potassium iodide solution. In Fig. III, 107, 2, a 250-300-ml. flask is
provided with two ground-glass joints at A and B; the tube from B
passes into a small conical flask containing potassium iodide solution;
C is a small tube containing glass beads moistened with potassium iodide
solution; the rest of the apparatus is self-explanatory. Weigh out
accurately about 02 g. of the finely powdered mineral * into a small
weighing-tube (1 cm. wide and 2 cm. long is a convenient size), and
introduce the tube and contents into the distillation flask; connect up
* Ridsdale's "Pyrolusite (Mn) Ore, No. 18" (one of the Analysed Samples for
Students) or the Bureau of Analysed Samples" Manganese Ore, No. 176 " (one of the
British Chemical Standards) is suitable.
"l'uunHTaTwe lnorgamc Analysis
the apparatus as shown in the figure. Introduce 100 ml. of water con-
taining 35 g. of iodate-free (e.g., A.R.) potassium iodide into the absorp-
tion apparatus, which should be immersed in cold water. Place
25 ml. of concentrated hydrochloric acid into the separating-funnel,
and add it to the contents of the flask; meanwhile maintain a very slow
stream of carbon dioxide through the apparatus. Heat the mixture
very gently so that chlorine is slowly evolved. Increase the tempera-
ture gmdnally to the boiling point, and finally pass a slow current of
carbon dioxide through the boiling solution until all the chlorine has
been expelled (about 15 minutes). Immediately before the heating is
stopped, increase the current of carbon dioxide in order to prevent the
solution in the absorption vessels from passing back into the flask.
Disconnect the absorption vessels. With the apparatus of Fig.. III,
107, I, the contents of the U-tubes are quantitatively transferred to a
conical flask; with the apparatus of Fig. III, 107, 2, the tubes and
beads are well rinsed with water and removed from the flask. Titrate
the liberated iodine at once with standard O'IN -sodium thiosulphate
in the usual manner. If desired, the solution may be made up to 100
ml. in a volumetric flask, and 50-ml. portions titrated with the sodium
thiosulphate solution; if this procedure is adopted, the weight of the
mineral may be increased to 0,3-0,4 g.
Calculate the percentage of Mn02 in the mineral.
1 ml. N-Na 2S 20 3 == 004347 g. Mn02
Note. Red lead Pb 3 0 4 and lead dioxide PbO z may be estimated in a.
similar manner (compare Section III, 57, Note).
III, 108. Determination of chlorates and of bromates.-Discussion.
Chlorates and bromates may be determined by the distillation process
described in the previous Section for pyrolusite. The process of 'distil-
lation may be avoided in these and similar cases * by mere digestion
with hydrochloric acid and potassium iodide solution at an elevated
temperature; decomposition is quantitative.
KCI0 3 +
6HCI = KCI + +
3Cl z 3H 20
3Cl 2 + 6KI = 6KCl +
31 2
Na 2S20 3 == I == KC10 3 /6 == KBr0 3 /6
A strong bottle (" pressure bottle ") with a very accurately ground
stopper is necessary: Generally, the ordinary stoppered bottle of
commerce is not sufficiently tight, and it is better to re-grind the stopper
with a little very fine emery and water. It must then be tested by
securing the stopper tightly and immersing in hot water; if any bubbles
of air pass through the stopper, the bottle is useless. The stopper may
be secured by means of fine copper wire threaded through a piece of
* For example, chromates and dichromates. These yield the green chromic chloride
and an equivalent quantity of iodine:
2K 2 CrO,+ 6K1+ 16HCI = lOKCI+ +
2CrCI. +
31 2 SH2 0
+
K 2 Cr 2 0 7 6K1+ 14HCI = SKCI+ +
2CrCI. +
31. 7H 2 0
Here it is necessary to dilute the solution very considerably in order to prevent the
green colour of the chromic salt from masking the blue colour of the starch in the
subsequent titration with standard sodium thiosulphate solution.
1 m!. N.Na.S 2 0 a "" 006474 g. K.Cr0 4 "" 004904 g. K.Cr.07
Volumetric Analysis 347
rubber tubing securely fixed to the neck of the bottle, or by means of a.
special screw clamp (Fig. III, 108, 1) *
For practice, the student may determine the percentage of CI0 3
(or of Br0 3 ) in potassium chlorate (or potassium bromate), preferably
of A.R. quality.
Procedure. Weigh out accurately 025-0'30 g. ofthe finely powdered
potassium chlorate into a pressure bottle, add 7 g. of iodate-free
potassium iodide dissolved in a small volume of water,
and displace the air from the bottle by means of
carbon dioxide from a Kipp's apparatus or from a
cylinder. A<;ld 25 ml. of concentrated hydrochloric
acid, insert the stopper, fasten it down securely, and
wrap the bottle in a thick duster. Immerse the whole
in cold water in a water-bath, heat the water gradu-
ally to boiling, and continue the boiling for 1 hour.
Allow the water to cool, and when quite cold, re-
mOve the bottle, open it, transfer the contents
quantitatively into a 250-ml. volumetric flask, and
make up to the mark. ~ Shake well. Titrate 50-ml.
portions with standard O'IN-sodium thiosulphate,
using starch as indicator.
Calculate the percentage of CI0 3 in the sample of
potassium chlorate.
1 ml. N-Na 2S 20 3 == 011391 g. CI0 3
== 002043 g. KCI0 3
III, 109. Volumetric determination of lead.-Dis-
cussion. The lead is precipitated as the chromate FIG. III, 108, l.
with potassium chromate or dichromate solution in
a medium buffered with a mixture of acetic acid and sodium or
ammonium acetate. The precipitate is washed with water, dissolved
in dilute hydrochloric acid, treated with potassium iodide solution, and
the liberated iodine titrated with a standard solution of sodium
thiosulphate.
Pb(C 2H 3 0 2 )2 +
K 2CrO 4 = PbCrO 4 +
2KC 2H 3 0 2
PbCrO 4 + 2HCI = H 2CrO 4 + PbCI 2
2H 2Cr0 4 + 6KI +
12HCl = 2CrC1 3 +
(iKCl 31 2 + +
SH 2 0
Thus Pb == 31
or
Another method, which is sometimes used, consists in adding excess
of OIN -potassium dichromate to the solution buffered with alkali
acetate, boiling for 2-3 minutes, filtering the precipitate on'a sintered-
glass or porous-porcelain crucible, washing the precipitate well with
cold water, and determining the excess of dichromate in the cooled
filtrate either iodometrically by the addition of excess of potassium
iodide and titration with standard thiosulphate solution or with stand-
ard ferrous ammonium sulphate solution.
For practice, the student may determine the percentage of lead in
lead nitrate, preferably of A.R. purity.
* Such bottles may be purchased, for example, from A. Gallenkamp and Co., Ltd.,
London, E.C.2, England, or from the Fisher Scientific Co., Pittsburgh, Pa., U.S.A.
341; (Juantitative Inorganic Analysis
Procedure. Weigh out accurately about 03 g. of A.R. lead nitrate,
dissolve it in excess of dilute acetic acid (1 : 4), and add 2g. of sodium
acetate; * dilute to 150 ml. Heat the solution to boiling, and add
from a pipette 10 m!. of hot 4 per cent potassium chromate solution.
Boil gently for 5-10 minutes, filter the lead chromate through a sintered-
glass or porous-porcelain crucible, and wash several times with dilute
sodium acetate solution. Transfer the precipitate quantitatively to a
250-m!. conical flask, dissolve it in dilute hydrochloric acid (1 : 1), add
20 m!. of 10 per cent potassium iodide solution and stir gently. 'Titrate
at once with stapdard O'IN -sodium thiosulphate until the iodine colour
has nearly disappeared, add 2 m!. of starch solution, and continue the
t.itration until the colour of the solution changes to a clear green.
Dilution facilitates the detection of the end point.
Calculate the percentage of lead in the sample of lead nitrate.
III, 110. Analysis of hydrogen peroxide.-Discussion. Hydrogen
peroxide reacts with iodide in acid solution in accordance with the
equation:
HzOz +2H+ +
21- = 12 +
2H 2 0
The reaction velocity is comparatively slow, but increases with increas-
ing concentration of acid. The addition of 3 drops of a neutral 20 per
cent ammonium molybdate solution renders the reaction almost
instantaneous, but as it also accelerates the atmospheric oxidation of
the hydriodic acid, the titration is best conducted in an atmosphere of
carbon dioxide.
The iodometric method has the advantage over the permanganate
method (Section III, 55) that it is less affected by stabilisers which are
sometimes added to commercial hydrogen peroxide solutions: These
preservatives are often boric acid, salicylic acid, and glycerol, and
render the results obtained by the permanganate procedure less
accurate.
Procedure. Dilute the hydrogen peroxide solution to 2-volume
strength (ca. 06 per cent HzOz). Thus, if a " 10-volume " hydrogen
peroxide is used, transfer 20 ml. by means of a burette or pipette to a
lOO-ml. volumetric flask, and make up to the mark. Shake well.
Remove 10 m!. of this diluted solution, and add it gradually and with
constant stirring to a solution of 2 g. of pure potassium iodide in 200
ml. of 2N -sulphuric acid (1: 20) contained in a stoppered bottle.
Allow the mixture to stand for 15 minutes, and titrate the liberated
iodine with standard OIN-sodium thiosulphate, adding 2 m!. of starch
solution when the colour of the iodine has been nearly discharged.
Run a blank determination at the same time.
Better results are obtained by transferring 10 mI. of the diluted
hydrogen peroxide solution to a conical flask, and adding 180 ml. of
2N (l: 20) sulphuric acid. Pass a slow stream of carbon dioxide
through the flask, add 20 mI. of 10 per cent potassium iodide solution,
followed by 3 drops of 20 per cent ammonium molybdate solution.
Titrate the liberated iodine immediately with standard 01 N -s'odium
thiosulphate in the usual way.
Repeat the titration with two other 10-ml. portions of the peroxide
solution.
* The addition of alkali acetate is essential only when potassium dichromate (e.g.,
10 m!. of the saturated solution) is used for precipitation.
Volumetric Analysis 349
Calculate the weight of H 20 2 in 1000 ml. of the original solution .
..
1 ml. N-Na 2Sz0 3 == 001701 g. HzO z
Note. The above method is available for all per-salts.
III, 111. Determination of the available chlorine in bleaching powder.
_Discussion. Bleaching powder consists essentially of a mixture of
calcium hypochlorite Ca(OCl)2 and the basic chloride CaCI 2,Ca(OH)2,H 20;
some free slaked lime is usually present. The active constituent is the
hypochlorite, which is responsible for the bleaching action. Upon
treating bleaching powder with acid, chlorine is liberated.
Ca(OCl)2 + 4HCI = CaC1 2 + 2C1 + 2H 20
2
K(SbO)C H 0 + 12 + 4NaHC0
4 4 6 3
= KNaC H 0 a + NaH Sb0 + 2NaI + H 0 + 4C0
4 4 2 4 2 2
Volumetric Analysis 351
This method is satisfactory for tartar emetic, antimony oxide, and
certain other antimony compounds, but fails when applied to alloys in
which antimony is not the principal constituent (5-20 per cent anti-
lllony). The potassium bromate method (Sections III. 135. 137) or the
permanganate method (Section III. 117) may then be used, and is, in
general, more satisfactory for the volumetric estimation of antimony.
For practice, the student may determine the percentage of antimony
in tartar emetic K(SbO)C 4H 4 0 6 ,0'5H 20 or in the anhydrous A.R.
potassium antimonyl tartrate.
Procedure (antimony in tartar emetic). Weigh out accurately about
2 g. of the finely powder~d A.R. tartar emetic (or 25 g of the hydrated
compound), dissolve it in water, and make up to 25 ml. in a volumetric
flask. Shake well. Transfer 50 ml. of the solution to a 250-ml.
co'nical flask by means of a burette (a pipette should NOT be used. for
antimony salts are nearly as poisonous as those of arsenic), add 20 ml. of a
cold saturated solution of pure sodium bicarbonate (about 10 ml. are
required to about 01 g. of Sb 20 3 ) and 2 ml. of starch solution. Titrate
with standard O'IN -iodine until the blue colour just appears. The titra-
tion must be carried out immediately after the sodium bicarbonate
solution is added, otherwise a portion of the metal is precipitated as
antimonious hydroxide, which reacts extremely slowly with the iodine.
Repeat the determination with two other 50-ml. volumes of the solution.
Calculate the percentage of antimony in the sample used.
1 ml. N-1 == 006088 g. Sb
III. 114. Determination of antimony in antimonic oxide and in anti-
monates.-Here the reaction is the reverse of tha t for the determination
of antinionious compounds;
Sb 20 5 + 4H+ + 41- ~ Sb 0 + 212 + 2H 0
2 3 2
and
H 2SOa + 4HI = 212 + S + 3H20
(c) oxidation of sulphite to sulphate.
In determinations of sulphurous acid and sulphites, excess of standard
OlN-iodine is diluted with several volumes of water, acidified with
hydrochloric or sulphuric acid, and a known volume of the sulphite or
sulphurous acid solution is added slowly and with constant stirring from
a burette, with the jet close to the surface of the liquid. The excess of
iodine is then titrated with standard O'lN -sodium thiosulphate. Solid
* A.R. antimony can be obtained from the Mallinckrodt Chemical Works, U.S.A., or
from the J. T. Baker Chemical Works, Phillipsburg, U.S.A.
Volumetric Analysis 355
soluble sulphites are finely powdered and added directly to the excess
of the iodine solution. Insoluble sulphites (e.g., calcium sulphite) react
very slowly, and must be in a very fine state of division.
For practice, the student may determine the percentage of
Na 2S03,7H 20 in the ordinary or A.R. crystallised product.
Procedure. Weigh out accurately about 025 g. of crystallised
sodium sulphite (1), and add it to a 350-ml. conical flask containing
25 ml. of standard OIN-iodine, 5 ml. of 2N-hydrochloric acid, and 150
wI. of water. Swirl or stir the liquid until all the solid has reacted, and
titrate the excess of iodine with standard O'lN -sodium thiosulphate
'using starch as indicator. Repeat the determination with two other
O25-g. portions of the sulphite.
Calculate the percentage of Na 2S0 3,7H 20 in the sample employed.
1 ml. N-1 == 003203 g. S02 == 01261 g. Na 2S0 3,7H 20
Note. 1. Alternatively, weigh out accurately about 25 g. of crystallised
sodium sulphite, dissolve it in boiled-out water, and make the solution up to
250 ml. in a volumetric flask with boiled-out water. Shake well. Use
25 ml. for each titration.
III. 119. Determination of hydrogen sulphide and sulphides.-
Discussion. The iodimetric method utilises the reversible reaction:
H 2S + 12 ~ 2H1 + S
For reasonably satisfactory results, the sulphide solution must be dilute -
(concentration not greater than 004 per cent or 0'02N), and the sulphide
solution added to excess of acidified O,oIN- or O-IN-iodine and not
conversely. Loss of hydrogen sulphide is thus avoided, and side
reactions are almost entirely eliminated. (With solutions more concen-
trated than about 002N, the precipitated sulphur encloses a portion of
the iodine, and this escapes the subsequent titration with the standard
sodium thiosulphate solution.) The excess of iodine is then titrated
against standard thiosulphate solution, using starch as indicator.
1 ml. N-1 == 001703 g. H 2S
Excellent results are obtained by the following method, which is of
wider applicability. When excess of standard sodium arsenite solution
is treated with hydrogen sulphide solution and then acidified with
hydrochloric acid, arsenious sulphide is precipitated:
AS 20 3 + 3H 2S = AS 2S3 + 3H 20
The excess of arsenious acid is determined with O'IN-iodine and starch
(compare Section III. l04A).
For practice, the student may determine the strength of hydrogen
sulphide water.
Procedure. Prepare a saturated solution of hydrogen sulphide by
bubbling the gas through distilled water. Place 50 ml. of standard
OlN -sodium arsenite into a 250-ml. volumetric flask, add 20 ml. of
the hydrogen sulphide water, mix well, and add sufficient hydrochloric
acid to render the solution distinctly acid. A yellow precipitate of
arsenious sulphide is formed, but the liquid itself is colourless. Make up
to the mark with distilled water, and shake thoroughly. Filter the
mixture through a dry filter-paper into a dry vessel. Remove 100 ml.
4!uanc~tatLVe 1 nOTganic Analysis
f the filtrate, neutralise it with sodium bicarbonate, and titrate with
, ~tandard aIN-iodine and starch to the first blue colour. The quantity
of residual arsenious acid is thus determined, and is deducted from the
original 50 ml. employed.
Calculate the concentration of the hydrogen sulphide in the solution.
1 ml. N-As z0 3 == 002556 g. HzS
III, 120. Determination oi ierricyanides.- Discussion. The reaction
between ferricyanides and potassium iodide is a reversible one:
2Ka[Fe(CN)6] + 2K1 ~ 2K [Fe(CN)6] + 12
4
and the ferro cyanide ions are thus removed from the sphere of action.
For practice, the student may determine the purity of potassium
ferricyanide, preferably of A.R. grade.
Procedure. Weigh out accurately about 10 g. of the potassium
ferricyanide and dissolve it in 250 ml. of water in a volumetric flask.
Pipette 25 ml. of this solution into a 250-ml. conical flask, add about
20 ml. of 10 per cent potassium iodide solution, 2 ml. of 2N-sulphuric
or hydrochloric acid, and 15 ml. of a solution containing 20 g. of
crystallised zinc sulphate. Titrate the liberated iodine immediately
with standard O'lN-sodium thiosulphate and starch; add the starch,
solution (2 ml.) after the colour has faded to a pale yellow. The titra-
tion is complete when the blue colour has just disappeared. \Vhen
great accuracy is required, the process should be conducted in an
atmosphere of carbon dioxide. Repeat the titration with two other
25-ml. portions of the solution. .
Calculate the purity of the salt.
1 ml. N-Na 2S 20 a = 03293 g. K 3[Fe(CN)6]
tIll, 121. Determination oi ierric iron (iodometric method}.-The
reaction:
2Fe+++ +
21- ~ 2Fe++ 1z +
is quantitative to the right-hand side if the iodine is removed by
titration with sodium thiosulphate solution, but is normally too slow
to be of practical utility. The addition of a little cuprous iodide,
however, acts as a catalyst and so accelerates the reaction that titration
may be carried out forthwith. The cuprous iodide is prepared as
follows. About 1 ml. of N-copper sulphate solution is treated with an
excess of 10 per cent potassium iodide solution (2-3 ml.) and the free
iodine is discharged by the addition of aqueous sodium thiosulphate in
the presence of starch solution. The precipitate is first thoroughly
washed by decantation, and then shaken with 20 ml. of water; about
1 ml. of the suspension thus obtained is used for a titration.
The ferric solution, slightly acid with hydrochloric acid and contain-
ing about 015 g. of Fe, is treated with 1 ml. of the cuprous iodide
suspension and sufficient 10 per cent potassium iodide solution, to give
Volumetric Analysis 357
a concentration of ca. 2 per cent, and shaken well. After 3-5 minutes
the whole is titrated with standard OIN -sodium thiosulphate to the dis-
appearance of the blue starch colour. The end point is fairly definite
and permanent, although the starch coloration re-appears more rapidly
than in the copper-thiosulphate titration (Sections III, 105-106).)<,
1 ml. N-Na 2S 2 0 3 == ,005584 g. Fe
Note. If A.R. ferric alum is employed, the method will serve as a useful
check for the standardisation of thiosulphate solutions.
OXIDATIONS WITH POTASSIUM IODATE
III, 122. General discussion.-A glance at the table of standard
oxidation potentials (Table XVI, Section I, 46) reveals the fact that
both potassium iodate and potassium bromate are stronger oxidising
agents than iodine. The reaction between potassium iodate and reduc-.
jng agents, such as potassium iodide or arsenious oxide, in weakly acidic
solutions, say OI-20N-hydrochloric acid, stops at the stage when the
iodate is reduced to iodine:
KI0 3 + 5KI + 6HCl = 6KCI + 312 + 3H 0
2
2KI0 3 + 5H3As03 + 2HCI = 2KCI + 5H 3As0 4 + 12 + H 20
Actually the iodate is first reduced to iodide, and the latter is subse-
quently converted into free iodine. This can readily be shown by
carrying out the oxidation of reducing substances in weak acid solutions
(01-2N-hydrochloric acid) containing mercuric sulphate; here the
iodide is converted into the fairly stable complex ion [HgI 4]- - as fast as
it is formed, and the reaction is accordingly arrested at the iodide stage.
An example is :
4KI0 3 + 12H3As03 + HgS04 (+ HCI)
= K 2S0 4 + K 2[HgI 4] + 12H3As04 (+ HCI)
In more concentrated hydrochloric acid solutions (exceeding 4N)
L. W. Andrews (1903) has shown that the iodate is reduced ultimately
to iodine mono chloride-the substance therefore acts as a very much
more powerful oxidising agent. Examples are :*
KI0 3 + 2KI + 6HCI = 3KCI + 3ICI + 3H 20
KI0 3 + 2H3As03 + 2HCI = 2H3As04 + KCI + ICI + H 20.
KI0 3 + 212 + 6HCI = KCI + 5ICI + 3H 2 0
In these reactions the iodine which is initially liberated is converted
into iodine chloride. Now both iodine and iodine chloride are brown-
ish-yellow in aqueous solution, but in organic solvents, such as carbon
tetrachloride or chloroform, iodine is purple whilst iodine chloride
remains yellow. The point at which the last trace of iodine disappears
may be determined by the change in colour from purple to yellow when
a few ml. of carbon tetrachloride or chloroform are shaken up in the
solution during the titration (compare Section 1,71, and Section 111,100).
The use of potassium iodate in the presence of high concentrations
of hydrochloric acid forms the basis of the Andrews procedure for
the determination of reducing agents. It has been applied by G. S.
Jamieson (1926)t and others to numerous quantitative determin-
ations. Essentially, all methods depend upon the reaction:
1- - 2.0 ~ 1+
, t For details of Lang's cyanide method, see W. Bottger and R. E. Oesper, Newer
Method8 of Volumetric Ohemical Analysis, 1938, p. 76 (Van Nostrand and Co. or Chapman
II.Ild Hall), and F. Sutton and A. D. Mitchell, A Systematic Handbook oj Volumetric
Analysis, 1935 (J. and A. Churchill).
360 Quantitative Inorganic Analysis
assay value of better than 999 per cent. The titraticns are carried out
in glass-stoppered bottles or flasks of 250 or 300 ml. capacity in the
presence of a high concentration of hydrochloric acid, otherwise hydro-
lysis of the iodine monochloride is liable to occur. The solution to be
titrated should contain so much hydrochloric acid that, even after all
the titrating solution has been added, the acidity is at least 4N; that
is, at least one-third, and preferably one-half, of the solution should
consist of concentrated acid. The end point is detected by the loss of
the last trace of purple (violet) colour from a layer of 5 ml. of chloroform
or carbon tetrachloride when shaken with the liquid. When a titration
has actually been completed, there is no return of the iodine colour
even after keeping the solution for a day. Iodate titrations can be
made in the presence of filter-paper, alcohol, formaldehyde, saturated
organic acids, as well as many other kinds of organic matter.
The use of carbon tetrachloride or chloroform as an indicator for the
disappearance of the last trace of iodine gives good results, but a glass-
stoppered bottle or flask must be employed, since the reaction mixture
must be shaken near the end point. The titration may be carried out
in an open beaker (say, of 400.ml. capacity) or in a conical flask in the
presence of an irreversible indicator, such as Amaranth, Brilliant Ponceau
5R, or Naphthol Blue Black * (G. F. Smith, 1942). The indicators are
employed in 02 per cent aqueous solution, and about 05 mI. is utilised
per titration; the indicator blank is equivalent to 005 ml. of O'IN-
potassium iodate per 1 ml. of indicator and is therefore negligible.
The indicators are irreversible and are destroyed at the completion of
the reaction. The tendency of the indicators to fade as the equivalence
point is reached is counteracted by delaying their addition until most
of the iodine has disappeared from the solution upon the introduction
of the standard iodate solution; the addition of a drop or two of indi-
cator just before the end point is recommended. Amaranth or Brilliant
Ponce au 5R may replace carbon tetrachloride or chloroform in the
determinations described in Sections III, 125-134.
No really satisfactory reversible redox indicators are yet available,
although p-ethoxychrysoidine (01 per cent solution in alcohol) is pro-
mising for the determination of trivalent arsenic; t the indicator
blank is equivalent to about 02 ml. of OIN-potassium iodate. The
indicator is added after the colour of the iodine commences to fade;
near the end point the colour changes to deep purple, and the titration
is then carried out slowly until the colour changes to orange.
III, 123. Preparation of OlN (O025M)-potassium iodate.-Dry some
A.R. potassium iodate at 120 0 C. for I hour and allow it to cool in a
desiccator. Weigh out exactly 5351 g. of the finely powdered potas-
sium iodate on a watch glass, and transfer it by means of a clean camel-
hair brush directly into a dry I-litre volumetric flask. Add about
400-500 ml. of water, and gently rotate the flask until the salt is
completely dissolved. Make up to the mark with distilled water.
Shake well. The solution will keep indefinitely.
* Amaranth (British Colour Index, No. 184), Brilliant Ponceau 5R (B.C.L, No. 185)
and Naphthol Blue Black (B.C.L, No. 246) of indicator quality may be obtained, for
example, from the G. Frederick Smith Chemical Co., 867 McKinley Avenue, Columbus,
Ohio, U.S.A., or from Eimer and Amend, 635 Greenwich Street, New York, 14, N.Y., or
from Fisher Scientific Co., 717 :Forbes St,reet, Pittsburgh 19, Pa., U.S.A. The action of
Naphthol Blne Black is somewhat slow at the end point.
t Private communication from R. Belcher, F.R.I.C.
Volumetric Analysis 361
It must be emphasised again that the solution is OIN only for the
reaction:
,
E
OXIDATIONS WITH CHLORAMINE-T
III, 140. General discussion. Preparation and standardisation. of
O1N solution.-Chloramine-T is the sodium derivative of N -chloro-p-
toluenesulphonamide CH 3CsH 4 S0 2NClN a,3H 2 0 (molecular weight,
28170), and is obtainable commercially in a high state of purity; it
is a by-product in the manufacture of saccharin. The aqueous solution
reacts as if it were a hypochlorite, and it has the great advantage that
it is far more stable than sodium hypochlorite solution:
CH 3 C6H 4 S0 2NClNa + H 20 ~ CHa,C6H4S02NH2 + NaOCl
Chloramine-T was introduced as a volumetric reagent by A. Noll
(1924) as a cheap substitute for iodine in the determination of trivalent
arsenic and antimony. The reagent reacts in dilute acid (3-5 per
cent) solution; if the acid is too concentrated, secondary changes
occur.
Chloramine-T reacts with potassium iodide in acid solution to liberate
iodine:
CH aCsH 4 S0 2NCINa + 2K1 + 2HCI
= CH3,C6H4S02NH2 + 12 + NaCI + 2KCI
The equivalent weight is therefore i moL, or 281'70/2, or 14085.
Reaction also occurs quantitatively with arsenious acid:
2CH aC6 H 4S0 2NCINa + AS 0 + 2H 0
2 3 2
. = 2CH3,C6H4S02NH2 + As 20 S + 2NaCI
Prepare an approximately O'IN solution of chloramine-T by dissolving
145 g. of the purest commercial product in I litre of water. It may be
standardised by one of two methods.
1. Treat 25 ml. of the chloramine-T solution with 2 ml. of 2N-hydro-
chloric acid and 10 ml. of 10 per cent potassium iodide solution. Titrate
the liberated iodine with standard O'IN-sodium thiosulphate in the
usual way, using 2 ml. of starch as indicator.
2. Add the chloramine-T solution from a burette to 25 ml. of standard
OIN -arsenious oxide, containing a small crystal of pure potassium
iodide and 1 ml. of starch solution, until a permanent blue colour just
appears.
-. ,
,
MISCELLANEOUS VOLUMETRIC DETERMINATIONS
III. 145. Determination of zinc with standard potassium ferro cyanide
solution.-Discussion. Zinc ions in neutral or acid medium react with
potassium ferrocyanide solution to form the very sparingly soluble
potassium zinc ferrocyanide :
3Zn++ + 2K 4 [Fe(CN)6] = K 2Zn a[Fe(CN)6]2 + 6K+
Formerly the end point of the reaction was determined by means of
external indicators, such as uranyl nitrate and ammonium molybdate.
The acidified zinc solution was slowly titrated at 60-80 C. with the
ferrocyanide solution until a drop of the solution, brought into contact
with a drop of uranyl nitrate solution on a white spot plate, gave a
light-brown colour (due to the formation of uranyl ferrocyanide). In
recent years the external indicator has been replaced by the more
convenient internal indicator (diphenylamine, diphenylbenzidine, or
sodium diphenylamine sulphonate). The latter substances are oxida-
tion-reduction indicators, and are therefore dependent for their action
upon the ratio of the concentration of ferricyanide to ferrocyanide in
the solution (compare Section I. 50). A 0'05M-potassium ferro cyanide
solution, to which 03 g. of potassium ferricyanide per litre is added, is
employed; the solution is accordingly approximately O'OOIM with
respect to ferricyanide. The oxidation potential of a ferrocyanide-
ferricyanide electrode is given by the equation (Section I. 48) :
E = EO + 00591 log _[{Fe(CN)6}---]
[{Fe (CN)6} ]
(at ')5 C)
.. .
As long as excess of zinc ions remain in solution, the concentration of
the ferrocyanide is very small, and the potential is large. As soon as
the zinc ions are quantitatively precipitated, however, the next drop of
ferrocyanide solution causes a sudden increase in [{Fe(CN)6}- - - -], and
hence a sudden decrease in the oxidation potential. The end point
may therefore be detected by any of the three indicators mentioned
above. We may also titrate in the reverse manner; the method can
therefore be used for the titration of ferrocyanides by means of standard
zinc solution.
In this determination it is essential to work, so far as possible, under
uniform conditions, if concordant results are to be obtained. The
titration must not be carried out too rapidly, and the solution must be
thoroughly shaken throughout the titration, otherwise over-titration
may easily occur. Nitrates, oxidising agents, lead, copper, cadmium,
iron, manganese, nickel, and cobalt must be absent.
p-Ethoxychrysoidine (0'2 per cent solution in 1 : I sulphuric acid)
has been recommended as an indicator for this titration. Excellent
results are obtained by potentiometric titration (Chapter VI) in the
presence of excess of ammonium sulphate.
Procedure. Preparation of O05M-potassium ferrocyanide. Weigh out
21'12 g. of A.R. potassium ferrocyanide K 4 [Fe(CN)6J,3H 20 and 03 g.
of A.R. potassium ferricyanide, dissolve them in boiled-out water
379
380 Quantitative Inorganic Analysis
or in "equilibrium" conductivity water (Section II, 100), and make
up to 1 litre in a volumetric flask.
If the potassium ferro cyanide is pure:
1 m!. 0'05M-K 4[Fe(CN)6] == 0004904 g. Zn
Standardisation of the potassium ferrocyanide solution. Prepare a 0'1M-
zinc solution by weighing out either 16345 g. of A.R. zinc or 20345 g.
of ignited A.R. zinc oxide, dissolving either in dilute sulphuric acid,
and making up to 250 ml. in a volumetric flask. If exact weights are
not employed, the exact concentrations may be calculated from the
weights used.
Pipette 25 ml. of the zinc solution into a 250-350-ml. conical flask,
add 50 ml. of water, 25 ml. of 7N-sulphuric acid, 10 g. of ammonium
sulphate, and several drops of diphenylbenzidine solution (Section
III, 63). * Titrate the cold solution slowly and with vigorous shaking'
until the colour change from blue-violet to pale green is permanent.
Repeat the titration with two other 25-ml. portions of the zinc solution.'
Calculate the volume of the potassium ferrocyanide solution
equivalent to 001 g. of zinc, and compare this with the value deduced
from the actual weight of A.R. potassium ferrocyanide used.
:For further practice in this estimation, the student may determine
the percentage of zinc in crystallised zinc SUlphate, preferably of A.R.
quality, or of zinc in commercial zinc oxide. The sample must be
treated exactly as in the standardisation.
III,146. Determination of phosphorus.-Discussion. The phosphorus
must be in the form of orthophosphate. Upon treatment at
20-45 C. with a large excess of ammonium molybdate solution
in the presence of nitric acid, ammonium phosphomolybdate
(NH",hP04,12Mo03,2HN03,Hz.O is precipitated; this is converted
into (NH4hPO 412Mo03 or (NH 4MPMo 12 0 40] when suitably washed
with dilute potassium nitrate solution. The phosphorus in the washed
precipitate may be determined in one of three ways.
A. It may be titrated against standard sodium hydroxide solution
with phenolphthalein as indicator. The following reaction is assumed
to take place :
(NH4)3P04,12Mo03 23NaOH +
= IINa 2MoO", +
(NH4)2MoO", +
Na(NH",)HP0 4 IIH 20 +
whence 1 m!. N-NaOH == 0001349 g. P == 0003088 g. P 2 0 S
B. The precipitate is dissolved in dilute ammonia solution, sulphuric
acid added, and the resultant solution passed through a Jones reductor
(the molybdenum is thus reduced to the tervalent state) into excess of
ferric alum solution. The ferrous salt is titrated with standard O'IN-
potassium permanganate .
. (NH",h[PMo 120 40] + 39H 2S0 4 + 18Zn(Hg)
= 6M0 2 (S04)3 + +
3NH 4HS0 4 H 3P0 4 + 18ZnS0 4 + 36H2 0
5M0 2 (S04h + 6KMn0 4 +16H 20
= 10H 2MoO 4 + +
3K 2SO 4 6MnSO 4 + 6H 2SO 4
1 m!. N-KMn04 == 00008605 g. P
* If diphenylamine is used, 3 drops of the indicator are added; with more of the
indicator, the results are low. The amount appears to be immaterial (up to 10 drops)
for diphenylbenzidine:
Volumetric Analysis 381
since P =0 12Mo0 3 , which is equivalent to 18 atoms or 36 equivalents
of oxygen. .
G. The washed- precipitate is dissolved in dilute ammonia solution
a,nd the. molybdenum is precipitated as molybdyl oxinate M00 2(C 9H 6 0N)2'
The latter may be weighed after drying at 130-140 C., or it may be
titrated with standard potassium bromate solution (Section III, 137).
Arsenic precipitated with ammonium phosphomolybdate does not
affect the results: this constitutes an advantage of this procedure over
that of A and also that of weighing phosphorus as magnesium pyro-
phosphate (Section IV, 65).
Procedure. Prepare the molybdate reagent as follows. Dissolve
100 g. of A.R. molybdic anhydride or U8 g. of A.R. molybdic acid
(ca. 85 per cent Mo0 3 ) in a mixture of 400 ml. of water and 80 ml. of
concentrated ammonia solution; filter, if necessary. Add the molyb-
date solution thus obtained slowly and with constant stirring into a
solution containing 400 mI. of concentrated nitric acid and 600 mI. of
water; the end of the tube carrying the molybdate solution should
dip under the surface of the dilute nitric acid. Keep the mixture in a
warm place for several days, or until a portion heated to 40-45 C.
deposits no yellow precipitate. Decant the solution from any sediment
and preserve in glass-stoppered bottles. _
For practice in this estimation, the student may determine the per-
centage of phosphorus in anhydrous sodium phosphate Na 2HP0 4 , pre-
f~rably of A.R. grade: this should be dried for 1 hour at 120 C. and
allowed to cool in a desiccator before use. Weigh out accurately
02-025 g. of anhydrous sodium phosphate, dissolve it in water, and
dilute to 250 mI. in a volumetric flask. Shake welL. Transfer 25 m],
of the solution into a 250-350-ml. conical flask, dilute to 100 ml., and
add 12 g. of pure ammonium nitrate; shake until the solid dissolves.
Add 75 ml. of the molybdate reagent, previously warmed to 40-45 C.,
slowly using a tap funnel or a drawn-out funnel, and shaking con-
tinuously. It is important not to heat above 45 C. in order to avoid
contamination of the precipitate with molybdic anhydride. Fit the
flask with a rubber stopper, shake vigorously for 10 minutes, and allow
to stand for 30 minutes. Filter the prBcipitate through a quantitative
filter-paper. Wash the flask and the prBcipitate with 1 per cent
potassium nitrate solution until the filtrate will not decolorise 1 mI. of
water containing 1 drop of O'IN -sodium hydroxide and 1 drop of
phenolphthalein; this will require about 100 mI. of the washing liquid.
Place the paper and precipitate in the original flask. Complete the
determination by either of the following methods.
A. Treat the precipitate (NH 4 MPMo 12 0 40J with a slight ex()ess of
O'IN carbonate-free sodium hydroxide (say, 50 mI.). Stopper the
flask and shake; if all the precipitate does not dissolve, a further
quantity of standard alkali solution must be added. Dilute to approxi-
mately 150 mI., add 5 drops of phenolphthalein indicator, and titrate
with standard OIN-hydrochloric acid until the pink colour is com-
pletely discharged. Complete the titration by adding standard alkali
until the re-appearance of the pink colour.
Calculate the volume of standard alkali which has reacted with the
precipitate, and thence the percentage of phosphorus in the original
salt.
B. Dissolve the precipitate in 3N-ammonia solution, and add excess
382 Quantitative Inorganic Analysis :1
\
of sulphuric acid until the concentration of the latter is about 2N.
}Jass the solution at once through a Jones reductor (Section III. 51B)
into 50 ml. of A.R. ferric alum solution (100 g. of A.R. crystals, and
25 ml. each of concentrated sulphuric acid and syrupy phosphoric acid
in 1 litre). Wash with about 200 mi. of water, and titrate the ferrous
salt with standard O'lN-potassium permanganate. Carry out a blank
on the acid, water, and ferric alum solution.
C. Dissolve the washed precipitate (NH4)3[PMo12040] in 6N-
ammonia solution (about 20 mI.), add ca. 5 g. of ammonium acetate,
dilute to about 200 mI., then add a slight excess of a 5 per cent solution
of oxine in acetone, followed by 20-30 ml. of glacial acetic acid. Heat
to boiling, stir for 3 minutes, filter through a sintered-glass or porous-
porcelain crucible, and wash the precipitate with hot water. Dry the
precipitate to constant weight at 130-140 C. The phosphorus content
is computed from:
P = 0006202 X Weight of M00 2(C 9H 6 0N)2
Alternatively, titrate the molybdyl oxinate with O'lN-potassium
bromate, following the experimental details of Section III, 13,(.
Calculate the percentage of phosphorus in the original solid.
III. 14,(. Determination of temporary and permanent hardness of
water.-Discussion. Waters are described as "soft" or "hard"
according to their action upon soap. A water is said to be " soft" if
it gives an immediate lather with soap solution, and" hard" if a lather
is obtained with difficulty. Hardness is due almost entirely. to the
presence of calcium and magnesium ions; these combine with the
anions of the soap (usually sodium or potassium salts of oleic, palmitic,
or stearic acids) to form insoluble calcium and magnesium compounds.
The actual salts present in hard water are the bicarbonates, chlorides,
and sulphates of calcium and magnesium.
Upon boiling hard water, the bicarbonates are decomposed with the
precipitation of the normal carbonates:
Ca(HC0 3 h = CaCO a + H 20 + CO 2
and cooled distilled water. Filter through a dry filter, and determine
the hardness in the filtrate by titration with standard soap solution.
Determination of temporary hardness. The difference between the
total hardness and the permanent hardness gives the temporary hard-
ness of the water.
Procedure B. Titration method. Place 500 ml. of the water, or a
smaller volume (250 or 100 ml.) if the water is very hard, into a large
evaporating-dish or casserole, add a few drops of methyl orange or,
preferably, methyl orange-indigo carmine indicator, and add standard
O'1N -hydrochloric acid from a burette until the end point is reached.
It is advisable to add the same amount of indicator to 500 ml. of distilled
o
yuant~tat'/,Ve 1 norganic Analysis
water and introduce the standard acid until the "acid" colour is
produced. The tint can then be matched by that of the water under
examination; the blank correction is also determined at the same time.
Subtract the blank correction from the volume of standard acid used,
and thence calculate the corresponding weight of CaCO s and convert it
into parts per 100,000.
Ca(HCOS)2 + 2HCI = CaCl 2 + 2H 20 + 2C0 2
i.e., I m!. o'IN-HCI == 0005005 g. CaCO s
Note. The number of ml. of acid used is often regarded as the temporary
hardness. This, however, includes some calcium carbonate which would
remain in solution after boiling, and it is better to term it the alkalinity.
An empirical deduction of 04 ml. for O'IN -acid is then made to allow for
the solubility of the calcium carbonate, and the difference represents
temporary hardness.
Determination of permanent hardness. Measure out 250 m!. of the
water into a conical flask, best of Pyrex glass, and boil for 30 minutes.
Add an excess (say, 50 m!.) of standard OIN-sodium carbonate, and
evaporate to dryness on the water-bath. Take up the residue in a
little boiled-out distilled water, filter through a dry quantitative filter-
paper, and wash the residue four times "''1th hot water. Allow the
filtrate to cool, and make it up to 250 m!. in a volumetric flask with
boiled-out distilled water. Titrate 50 or 100 ml. with standard O'lN-
hydrochloric acid, using methyl orange or better, methyl orange-
indigo carmine indicator.
Calculate the volume of residual O'IN -sodium carbonate, and from
this the volume of O'IN-sodium carbonate consumed in precipitating
the alkaline-earth salts of the strong acids. . .
CaS0 4 + Na 2CO S = CaCO s +
Na 2S0 4
MgCl 2 + N a 2CO s = MgCO 3 + 2NaCI
I ml. 0IN-Na 2CO a == 0005005 g. CaCO s
Calculate the permanent hardness of the water (parts of CaCO s per
100,000).
III, 148. Determination of the hardness of water (" didiette" or
" Trilon B" method).-Discussion. The determination of the total
hardness of water by titration with standard soap solution as described
in the preceding section is, at best, subject to appreciable error owing
to uncertainty in the end point. The introduction of disodium di-
hydrogen ethylenediamine tetra-acetate (disodium dihydrogen versen-
ate)* by G. Schwarzenbach (1946) has rendered the determination both
facile and accurate. The reagent forms soluble complex ions with
calcium and magnesium ions.
Ethylenediamine tetra-acetic acid behaves virtually as a strong
dibasic acid, and it is usually represented (G. Schwarzenbach, 1947) as
a betaine structure:
" The author suggests the abbreviation" didiette," formed from the first two letters
of each of the four parts of the full chemical name, be used. The commercial name for
the dihydrate is " Trilon B."
Volumetric Analysis
The dihydrogen versenate ion reacts with calcium and with magnesium
ions to form complex ions:
Ca++ + [H2V]-- ~ [CaV]-- + 2H+
The sample of water .is brought to a pH of 10 with an ammonium
chloride-ammonium hydroxide buffer solution, and a few drops of an
alcoholic solution of eriochromeschwartz T are added as indicator. The
latter forms a wine-red, slightly dissociated compound with magnesium
ions. As the titration with a standard solution of sodium dihydrogen
versenate proceeds, the calcium ions are first removed, then the
magnesium ions and finally, at the end point, the magnesium in the
wine-red magnesium-eriochromeschwartz T complex is extracted,
resulting in a sharp colour change from wine-red to blue.
It is usual to add a little magnesium chloride solution to the disodium
dihydrogen versenate solution before it is standardised in order to
ensure an adequate concentration of magnesium in the solution
being titrated to form the coloured magnesium-indicator complex
ion.
Procedure. Prepare the following solutions: *
Standard disodium dihydrogen ethylenediamine tetra-acetate (disodium
dihydrogen 'l:ersenate) solution. Dissolve 4 g. of the solid reagent in 1
litre of distilled water and add 5 ml. of OIM-magnesium chloride
solution.
Indicator solution. Dissolve 5 g. of the indicator powder, consisting
of 1 part of eriochromt!sch~rtz T t and 9 parts of hydroxylamine
hydrochloride, in 100 ml. of methyl alcohol.
Buffer sol11.tion. Add 57 ml. of concentrated ammonia solution
(sp. gr. 0'88) to 675 g. of A.R. ammonium chloride, stir until dissolved,
and dilute to 100 ml.
Standard calcium chloride solution. Dissolve 1000 g. of A.R. calcium
carbonate in a little dilute hydrochloric acid, cool, and dilute to 1 litre
in a volumetric flask.
Place 50 ml. (or any other suitable volume) of the sample of water in
a Pyrex conical flask or in a porcelain evaporating-dish, add I ml. of the
buffer solution and 02 mI. of the indicator. Introduce the dis odium
dihydrogen versenate solution from a burette with continuous stirring
or shaking. Near the end point a slight blue coloration appears:
the end point is taken when the reddish tinge is completely discharged
and the solution has a pure blue colour.
Standardise the sodium dihydrogen versenate solution against 25-
50 ml. of the standard calcium chloride solution (1 ml. "" 0001 g.
CaC0 3) following the procedure given above.
Calculate the hardness of the sample of water (compare Section III,
147).
III, 149. Determination of sodium.-The sodium is precipitated as
NaZn(U02h(C2H302)9,6H20 or as NaMg(U02la(C2H302)9,65H20
(Section IV, 47B and 0), and the uranium determined according to
Section III, 91.
* Similar solutions are available from British Drug Houses, Ltd., Poole, Dorset, and
from tho Fisher Scientific Co., Pittsburgh.
t The British equivalent of eriochromeschwartz T (Eriochrome Black T) is Solochrome
Black \VDFA, and is manufactured by Imperial Chemical Industries Ltd., Dyestuffs
Division.
;'$~~ Quantitative Inorganic Analysis
III, 150. Determination of potassium.-The potassium is precipitated
as K 2Na[Co(N0 2)6] (Section IV, 480), and the nitrite in the
precipitate determined with ceric sulphate (Section III, 'i8).
III, 151. Determination of cadmium.-The cadmium is precipitated
as the ~-naphthaquinoline complex [(C13H9NhH2]CdI4 (Section IV,
18B). The precipitate is decomposed with ca. 20 mI. of 2N-ammonium
or sodium hydroxide, and the solution treated successively with 60 m!.
of 2N-hydrochloric or sulphuric acid, 5 ml. of 10 per cent potassium
cyanide solution (1), and 2 mI. of starch solution. The mixture is then
titrated with 0'025M-potassium iodate (Section III, 123) until the
starch is completely decolorised.
1 ml. 0'025M-KI0 3 == 0001405 g. Cd
Note. 1. The cyanide method possesses the advantage that the acidity
required is not so high as the other variation of the potassium iodate
titration. Iodine cyanide doc s not affect starch.
III, 152. Determination of ferric iron with standard mercurous per~
chlorate solution.*-Discussion. Mercurous perchlorate reduces the
ferric thiocyanate complex to the ferrous state; this forms the basis of
a method for the direct titration of ferric iron (compare Section III,
86). A large excess of thiocyanate must be added to the ferric salt
solution; the amount required depends upon the volume and the acid
concentration. For volumes of 100-200 mI., about 4-6 g. of potassium
or ammonium thiocyanate suffices, provided the solution does not
contain more than ca. 5 ml. of concentrated sulphuric acid or nitric
acid or 2-3 mI. of concentrated hydrochloric acid. Larger, amounts
of acids give high and erratic results; the solution must then be partially
neutralised. As a rule it is best to work with only slightly acid solu-
tions. The high concentration of thiocyanate prevents the precipita-
tion of insoluble mercurous salts. The disappearance of the'red colour
at the end point is relatively sharp. '
The reaction is not quite stoichiometric; in neutral or dilute acid
solution the amount of perchlorate needed is ca. 1 per cent higher than
is demanded by the stoichiometricr atio (the latter figure is readily
obtained by standardisation with sodium chloride, Section III, 26B).
The mercurous perchlorate solution should therefore be standardised
against a ferric solution of known concentration, containing a known
amount of acid. The procedure is said to be applicable to iron ores,
steel, pyrites, bauxite, etc. Phosphoric and acetic acids and their
salts give indistinct end points, and lead to high results.
Ferrous salts have no effect upon the reagent, and consequently a
mixture of ferrous and ferric salts may be determined. The ferric-iron
content of an aliquot part is first determined by the above method in
the presence of a little sulphuric acid (ferrous salts tend to be unstable
in hydrochloric acid solution); the ferrous-iron content is evaluated
by boiling another aliquot part with bromine water to oxidise it to
ferric iron, and the total ferric iron is titrated in the same way.
Procedure. Prepare an approximately OIN-mercurous perchlorate
solution.as detailed in Section III, 26; if the commercial red mercuric
oxide does not react readily with the perchloric acid and mercury, it
will be necessary to prepare the mercuric oxide by precipitation from
* W. Pugh, 1945.
Volumetric Analysis 389
mercuric chloride solution. Prepare also a 005M-ferric ammonium
sulphate soiution by dissolving 12055 g. of A.R. iron alum (molecular
weight = 96442) in water and diluting to 250 m!. in a volumetric flask;
check the concentration of the ferric iron ,by titration with OIN -potas-
sium dichromate. (Sections III, 67-68) or with OIN -ceric sulphate
(Section III, 77).
Standardise the mercurous perchlorate solution as follows. Treat
25 mI. of the 0'05M"ferric solution with 6 g. of A.R. potassium thio-
cyanate, dilute to 1.50 mI., add 1 mI. of concentrated hydrochloric acid,
and run in the mercurous perchlorate solution from a burette until the
red colour is discharged. Shake the mixture vigorously during the
titration; the approach of the end point is indicated by the fading of
the dark-red colour to a light orange. Henceforth the reagent should
be added dropwise, and a minute or so allowed between the drop
additions: it is advantageous to complete the titration at 60-70 C.
For further practice in the use of the reagent, the student should
determine the iron content of an iron ore. * Dissolve a suitable quan-
tity of the iron ore in concentrated hydrochloric acid, oxidise the ferrous
iron to the ferric state by adding an excess of bromine water and boiling,
boil off the excess of bromine, dilute to 150 mI., adjust the hydrochloric
acid concentration by the addition of ammonia solution so as not to
exceed the equivalent of 1 mI. of the concentrated acid, add 6 g. of
solid potassium thiocyanate, and titrate with mercurous perchlorate
solution as above and completing the titration at 60-70 C.
III, 153. Determination of zirconium as the normal selenite, Zr(Se0 3 )2' t
-Discussion. Zirconium may be precipitated in very dilute acid
solution with selenious acid as the basic selenite of somewhat variable
composition; upon digestion of the precipitate at 80-100 C. for 5-20
hours, it passes into the highly crystalline normal zirconium selenite
Zr(SeO a)2' The latter is filtered off, brought into solution, and the
selenium content determined as detailed in Section III, 62, Method B.
Procedure. The zirconium salt solution should not be more than
0'6N in sulphuric acid or hydrochloric acid (03N for small quantities,
< 10 mg.) or 0'35N in nitric acid; sulphate ions in high concentration
prevent complete concentration, but in 06N-hydrochloric acid and a
volume of 400 mI., 05 g. of sodium sulphate is permissible.
Treat the zirconium salt solution (200-300 mI.; 5-50 mg. of Zr) with
1-2 g. of pure selenious acid in the form of a 10 per cent solution, heat
to boiling, and leave on a hot-plate for 5-20 hours, i.e., until the
flocculent precipitate of basic selenite passes into the highly crystalline
normal selenite (1). Filter the precipitate through a quantitative
filter-paper, but first wash by decantation a few times with hot 05N-
hydrochloric acid, and finally wash with cold water until the filtrate
is free from selenious acid (2). Transfer the precipitate quantitatively
to the original vessel with the aid of a little cold water, then add 6 mI.
of 1 : 1 sulphuric acid and 5-10-mI. of 3 per cent sodium fluoride
solution; warm gently until the precipitate dissolves completely.
Transfer the solution to a 750-mI. conical flask, using a little warm
dilute sulphuric acid containing a few drops of sodium fluoride solution
* Either Ridsdale's " Iron Ore, No. 17 " (one of the Analysed Samples for Students)
or the Bureau of Analysed Samples" Iron Ore, ' A ' " (a British Chemical Standard) is
suitable.
t A. Claassen, 1939.
390 Q'uantitative Inorganic Analysis
to rinse out the original vessel (3). After cooling, dilute to 200-250 mI.,
add 10-15 ml. of 2 per cent starch solution, two portions of 02 g.
A.R. sodium bicarbonate to displace the air, followed by 20-40 ml. of
10 per cent potassium iodide solution (prepared from iodate-free
potassium iodide). After standing for 2 minutes, titrate the liberated
iodine with O'IN -sodium thiosulphate.
I mI. N-Na zS Z0 3 == 001140 g. Zr
Notes. 1. The period of heating required depends upon such factors a"
the temperature of the solution and the presence or absence of sulphuric
acid. The transformation is accelerated by sulphuric acid.
2. A test portion, acidified with sulphuric acid, should not liberate iodine
from potassium iodide-starch after 1 minute.
3. To prevent attack of the flask by dilute hydrofluoric acid, add a few
ml. of saturated boric acid solution. This is usually unnecessary.
III, 154. Determination of silica.*-Discussion. The compound,
which must be free from phosphate or arsenate, is fused with sodium
hydroxide, extracted with water, and the extract poured into excess of
hydrochloric acid. In this way the whole of the silica is brought into
solution as H 4Si0 4 :
Na 2Si0 3 + H 20 + 2HCl = H 4Si0 4 + 2NaCI
The solution is treated with a moderate excess of ammonium molyb-
date solution and with sufficient hydrochloric acid to give a final pH of
about 15, whereupon silicomolybdic acid forms rapidly:
H 4Si0 4 + I2(NH 4)zMo0 4 + 24HCl
= H 4[Si0 4,12Mo0 3] + 24NH 4CI + 12H 02
The method has the advantage of not introducing any metallic ions,
but it is essential to remove the excess of nitric acid (see Discussion
in Section IV, 6). The action is slower than by the fusion method.
Procedure. A. Dry Process. Dry some finely powdered pyrites *
at 100 C. for I hour. Fit an iron or nickel crucible into a hole in an
asbestos or " uralite " board sufficiently large to allow two-thirds of the
crucible to project below the board. Place about I g. of A.R. anhydrous
sodium carbonate into the crucible, and weigh accurately into it 04-
05 g. of the pyrites. Add 5-6 g. of sodium peroxide, and mix well
with a stout copper or nickel wire or with a thin glass rod. Wipe the
wire or rod, if necessary, with a small piece of quantitative filter-paper,
and add the latter to the crucible; cover the mixture with a thin layer
of peroxide. Place the crucible in the hole in the asbestos or " uralite "
sheet, and heat it with a very small flame. Increase the temperature
gradually until after 10-15 minutes the crucible is at a dull red heat
(the lower the temperature, the less is the crucible attacked) and just
sufficient to keep the mass completely fused. Remove the cover
occasionally and examine the contents; be sure that the whole mass is
fluid. Maintain the mitss fluid for 15 minutes to complete the oxidation.
Allow to cool, extract the crucible with water in a covered 600-ml.
beaker, rinse off the crucible-cover into the beaker, remove the crucible
* Ridsdale's "Iron Pyrites, No. 44aG'" (one of the Analysed Samples for Students)
is suitable.
406 Quantitative Inorganic Analysis
with a glass rod and wash it well; dilute to 300 mI. Boil the solution
for 15 minutes in order to destroy the excess of peroxide (Na 20 2 +
2H 2 0 = 2NaOH +
H 20 Z )' neutralise part of the alkali by adding
5-6 mI. of concentrated hydrochloric acid with stirring, add a 'What-
man "accelerator" or a quarter of an "ashless tablet," and filter
through a Whatman No. 541 filter-paper. 'Vash the residue at least
ten times with hot 1 per cent sodium carbonate solution. Acidify
the combined filtrate and washings contained in a 800-1000-ml.
beaker with concentrated hydrochloric acid, using methyl red or methyl
orange as indicator, and add 2 mI. of acid in excess. Dilute, if necessary,
to 600 mI., and heat to boiling. Precipitate the sulphuric acid by the
slow addition with stirring of a boiling 5 per cent solution of barium
chloride; the latter is added in slight excess of the calculated amount
required, assuming the pyrites to be pure FeS 2 Complete the deter-
mination as in Section IV, 6.
Calculate the percentage of sulphur in the sample.
B. Wet Process. Dry some finely powdered iron pyrites (1) at 100 C.
for 1 hour. Weigh out accurately 04-05 g. of the pyrites into a dry
400-ml. beaker, add 8 mI. of a mixture of 2 volumes of pure liquid
bromine and 3 volumes of pure carbon tetrachloride (fume cupboard !),
and cover with a clock-glass. Allow to stand in the fume cupboard for
15-20 minutes and swirl the contents of the beaker occasionally during
this period. Then add 15 mI. of concentrated nitric acid down the
side of the beaker, and allow to stand for another 15..... 20 minutes,
swirling occasionally as before. Heat the covered beaker below 100 C.
by placing it on a thick asbestos board over a steam-bath until all
action has ceased and most of the bromine, has been expelled (about 1
hour). Raise the clock-glass cover by glass hooks resting on the rim
of the beaker, or displace it to one side, * and evaporate the liquid to
dryness on the steam-bath. Add 10 ml. of concentrated hydrochloric
acid, mix well, and again evaporate to dryness to eliminate most of the
nitric acid. Place the beaker in an oven or in an air-bath at 95-100 O.
for 30-60 minutes in order to dehydrate any silica which may be present
~2). If the dry residue is heated at a temperature above 10/) C., loss
of sulphuric acid may occur and the determination will be rendered
useless. Moisten the cold, dry residue with 1-2 ml. of concentrated
hydrochloric acid and, after an interval of 3-5 minutes, dilute with 50
mI. of hot water, and rinse the sides of the beaker and the cover-glass
with water. Digest the contents of the beaker at 100 C. for 10 minutes
in order to dissolve all soluble salts. Allow the solution to cool for
5 minutes, and add 02-03 g. of aluminium powder to reduce the ferric
iron. Gently swirl (or stir) until the solution becomes colourless.
Allow to cool, add a 'Vhatman " accelerator," stir, and rinse down the
cover-glass and the sides of the beaker. Filter through a Whatman
No. 540 paper, and collect the filtrate in an 800-mI. beaker; wash the
filter thoroughly with hot water. Dilute the combined filtrate and
washings to 600 mI. and add 2 ml. of concentrated hydrochloric acid.
Precipitate the sulphate in the cold (3) by running in from a burette,
without stirring, a 5 per cent solution of barium chloride at a rate not
exceeding 5 mI. per minute until an excess of 5-10 mI. is present (4).
When all the precipitant has been added, stir gently and allow the
precipitate to settle for 2 hours, but preferably overnight. Filter
* This is llllllecessary if a Fisher" speedyvap " cover is used.
Gravimetric Analysis 407
through a No. 540 filter-paper or, preferably, through a porous-porcelain.
filter-crucible, wash with warm water until free from chloride, and
ignite to constant weight as described under A.
Calculate the percentage of sulphur in the sample.
Notes. 1. The procedure is applicable to most mineral sulphides; many of
these contain silica, and provision is made for the removal of this impurity
in the experimental details.
2. If the iron pyrites or the sample of sulphide contains no appreciable
proportion of silica, the heating at 95-100 C. may be omitted.
3. If a drop or two of stannous chloride solution is added to prevent re-
oxidation of the ferrous salt by air, precipitation of the barium sulphate may
be made in boiling solution according to the usual procedure (Section VI, 6).
4. Calculate the volume of 5 per cent barium chloride solution which must
be added from the approximate sulphur content of the iron pyrites FcS 2 or
of the mineral sulphide.
IV, 8. Determination of iron as ferric oxide.-Discussion. The
solution containing the ferric salt * is treated with a slight excess of
ammonium hydroxide solution to precipitate ferric hydroxide: t
FeCl 3 + 3NH 0H =
4 Fe(OHh + 3NH Cl 4
IV,14. LEAD
Discussion. Lead may be estimated in the following forms:
A. Lead sulphate, PbS0 4 This provides a separation from the numerous
elements which form soluble sulphates. Calcium, strontium, barium,
mercury, tungsten, silver, bismuth, antimony, and silica all interfere to a
greater or less extent. Hydrochloric and nitric acids exert a solvent action
upon lead sulphate, hence if these are present, the solution must be evaporated
twice with sulphuric acid until dense white fumes are evolved. Lead
sulphate is slightly soluble in dilute sulphuric acid, although with the
extremely dilute acid, the solubility is less than in water (00040 g. per litre
at 18 C.), owing to the common-ion effect; it is almost insoluble in alcohol.
A satisfactory wash solution is a dilute solution of sulphuric acid that has
been saturated with lead sulphate at the laboratory temperature.
At a red heat it is easily reduced by carbonaceous matter, with loss of
lead by volatilisation. For this reason the precipitate is best collected in a
filtering-crucible, and dried at 500-600 C.
B. Lead chromate, PbCr0 4 This determination is more accurate than A,
but is limited in its applicability because of the general insolubility of
chromates.
C. Lead molybdate, PbMo0 4 This is an excellent method, since the
substance has a high molecular weight, is less soluble than the sulphate, and
suffers no change upon ignition. Substances which form insoluble molyb-
dates (e.g., the alkaline-earth metals, copper, and cadmium), which are easily
hydrolysed (e.g., tin or titanium), and which form insoluble compounds with
lead (e.g., chromates, arsenates, or phosphates) must be absent.
D. Lead salicylaldoxime, Pb(C 7H 50 zN). Lead may be precipitated in
strongly ammoniacal solution (pH 93 or higher) with salicylaldoxime as the
lead salicylaldoxime complex Pb(C 7H 5 0 2N); it may thus be separated from
copper, nickel, cobalt, bismuth, iron, magnesium, manganese, and mercury,
the salicylaldoximates of which are not sufficiently soluble in ammoniacal
solution (see Section I, 62E).
E. Lead iodate, Pb(I0 3)2. Lead iodate is sufficiently insoluble in very dilute
nitric acid to make possible its use in the gravimetric and volumetric deter-
mination of the element. It may thus be separated from moderate amounts
of aluminium, manganese, zinc, cadmium, calcium, strontium, and mag-
nesium; titanium, zirconium, thorium, silver, mercury, bismuth, and
appreciable quantities of iron interfere.
F. Lead dioxide, PbO z This excellent electrolytic method is described in
Section IV, 79.
A. Determination of lead as sulphate. Procedure. Weigh out
accurately about 03 g. of the lead salt * into a lO-cm. porcelain basin,
dissolve it in about 20 ml. of water, add 2 ml. of pure concentrated
sulphuric acid, evaporate the mixture as far as possible on the water-
* A.R. lead nitrate is suitable. If the substance is insoluble in water, dissolve it in
the minimum quantity of nitric acid.
,
Gravimetric Analysis 421
bath, then on a sand-bath, wire-gauze, or low-temperature hot-plate
until thick white fumes of sulphuric acid are freely evolved. This
ensures the complete removal of nitric acid and conversion of the lead
salt into the sulphate. * Cool, dilute carefully with 40 ml. of water
(the ~nal solution shoul~ conta.in about 4 ml. of concentrated sulphuric
acid III 100 ml. of solutlOn), mlX thoroughly, and allow to stand for at
least an hour. Filter off the precipitate of lead sulphate through a
weighed porcelain or silica Gooch crucible or through a porous-porcelain
filtering-crucible. Wash the precipitate three times with 3 per cent
(by volume) sulphuric acid saturated with l()ad sulphate (compare
Section IV, 57A). Dry the crucible and contents at 100 C. for 1 hour,
and then place it inside a nickel crucible (Fig. II, 31, 4) and heat
gradually to a dull red heat (500-600 C.) ulltil constant weight is
obtained. Alternatively, the precipitate, collected on a sintered-glass
or porous-porcelain crucible and washed as above, may be washed with
rectified spirit until free from sulphate (1), and then dried at 130 C.
to constant weight. Weigh as PbSO 4 t
Calculate the percentage of lead in the sample.
Note. 1. For the rapid weighing of the lead sulphate, the alcohol washing
is followed by several washings with small volumef$ of anhydrous ether, and
the precipitate is sucked dry at the pump for 10 minutes. The outside of the
crucible is 'Ghen wiped with a clean linen cloth, left in a vacuum desiccator for
10 minutes, and weighed.
B. Determination of lead as chromate. Procedure (compare Section
II1,109). Weigh out 03 g. of the lead salt (I), dissolve it in 150 ml. of
water, and add dilute acetic acid to the solution until it is distinctly
acid. Heat to boiling, add from a pipette 4 per cent potassium chrom-
ate solution in slight excess (10 ml. will usually suffice). Boil gently
for 5-10 minutes (or until the precipitate settles); the supernatant
liquid must be coloured slightly yellow. Filter through a Gooch,
sintered-glass or porous-porcelain filtering-crucible, wash thoroughly
with a hot, dilute solution of sodium acetate Ot with hot water. Dry
at 120 C. to constant weight. Weigh as PbCr()4.
Note. 1. A.R. lead nitrate is suitable for practice in this estimation. If
the solution is neutral or basic, add acetic acid until it is distinctly acid. If
the solution contains nitric acid, add sufficient sodium acetate (5-10 g.) to
replace the nitric acid by acetic acid.
C. Determination of lead as molybdate. Procedure. Weigh out
03 g. of the lead salt, dissolve it in 200 ml. of water, and add 4 drops
of concentrated nitric acid. Heat to boiling, and slowly add from a
burette or pipette, with stirring, a 25 per cent aqueous solution of
ammonium para-molybdate. When precipitation appears to be com-
plete, boil for 1 minute, allow the precipitate to settle, and add a few
drops of the precipitant to the supernatant liquid. If a precipitate
forms, repeat the process until the ammonium molybdate is present in
slight excess. When precipitation is completi:l, add dilute ammonia
solution (1 : 2) dropwise until the solution is nelltral or slightly alkaline
to litmus. Acidify with a few drops of acetic acid, and allow to stand
* For work demanding the highest accuracy, allow to cool, wash down the sides of the
dish, and repeat the evaporation.
t The conversion factors for all the determinations descl'ibed in this and the following
Sections are collected in the Appendix (Section A, 2).
422 Quantitative Inorganic Analysis
for a few minutes. Decant the supernatant liquid through a weighed
porcelain or silica (Vitreosil) filter-crucible, and wash the precipitate 3
or 4 times by decantation with 75-mL portions of 2 per cent a;llmonium
nitrate solution. Transfer the precipitate to the filter, and wash until
the washings give no test for molybdenum (e.g., no brown precipitate
with potassium ferro cyanide solution). Place the filter-crucible inside
a nickel crucible (Fig. II, 31, 4) or upon a crucible-ignition dish, and
gradually heat to dull redness. Maintain the crucible at dull redness
for 10 minutes, cool in a desiccator, and weigh. Repeat the heating,
etc., until constant weight is attained. Weigh as PbMo0 4
D. Determination of lead as the salicylaldoximate. Procedure. To a
solution (ca. 25 mI.) of lead nitrate or lead acetate containing about
01 g. of Pb, add 10 mL of a freshly prepared 1 per cent salicylaldoxime
solution (for preparation, see Section I, 62E), dilute to 50 mL and add
125 mL of concentrated ammonia solution. Stir the resulting pre-
cipitate for 1 hour and allow to settle. Decant the supernatant liquid
through a sintered-glass crucible (porosity No.4), wash the precipitate
by decantation until free from salicylaldoxime (as shown by the absence
of a colour with ferric chloride solution), dry at 105 C. for 1 hour, and
weigh as Pb(C 7H 5 0 2N).
E. Determination of. lead as iodate. Procedtlire. The solution may
contain up to 03 g. of Pb (1) in 150 mL of water, and should preferably
be neutral. Add 4 mL of concentrated nitric acid, heat to boiling, and
introduce 25-30 ml. of 6 per cent iodic acid solution slowly and with
constant stirring. Continue stirring for 2 minutes after the iodic acid
reagent has been added, and keep at 60-70 C. for 30 minutes. Cool to
the laboratory temperature, filter through a sintered-glass crucible
(porosity No.3), wash the precipitate with 75 mL of 02 per cent iodic
acid in 1 per cent v Iv nitric acid, then with three 2-ml. portions of ice-
cold water, and finally twice with a little dry acetone. Draw air
through the precipitate (water-pump) for 5 minutes. Dry at 140 0 C.
to constant weight (about 1 hour). Weigh as Pb(I0 3 )2'
The lead may also be determined volumetrically as follows. Dissoh'e
the precipitate in hot 10 per cent sodium hydroxide solution (2), and
wash the filter with 2 per cent sodium hydroxide solution, Cool the
solution, add 4 g. of pure potassium iodide, then a large excess of con-
centrated hydrochloric acid, and titrate with standard O'IN -sodium
thiosulphate solution.
Notes. 1. About 045 g., accurately weighed, of dry A.R. lead nitrate may
be employed for practice in this determination.
2. A protective layer of lead chloride is formed with hydrochloric acid.
IV,15. SILVER
DisCWlsion. This element is usually determined as silver chloride, AgeL
The theory of the process has been given under Chloride (Section IV, 5).
Lead, cuprous, palladous, mercurous, and thallous ions interfere, as do
cyanides and thiosulphates. If a mercurous (or cuprous or thallous) salt is
present, it must be oxidised with concentrated nitric acid before the
precipitation of silver; this process also destroys cyanides and thiosulphates.
If lead is present, the solution must be diluted so that it contains not more
than 025 g. of the substance in 200 mI., and the hydrochloric acid must be
added very slowly.
Silver may also be detcrmined electrolytically; for details see Section IV, 83.
Gravimetric Analysis 423
Determination of silver as chloride. PrQcedure. The solution
(200 ml.) should contain about 01 g. of silver (I) and about I per cent
by volume of nitric acicL Heat to about 70 C., and add approximately
O.2N pure hydrochloric acid slowly and with constant stirring until no
further precipitation occurs; avoid a large excess of the. acid. Do not
expose the precipitate to too much bright light. Warm until the
precipitate settles, allow to cool to about 25 C., and test the super-
natant liquid with a few drops of the acid to be sure that precipitation
is complete. Allow the precipitate to settle in a dark place for several
hours or, preferably, oVfirnight. Pour the supernatant liquid through
a weighed Gooch, sin1jered-glass or porous-porcelain crucible, wash
the precipitate by decantation with O'IN -nitric acid, transfer the pre-
cipitate to the crucible, and wash again with O'OIN-nitric acid until
free from chloride.' Dry the precipitate first at 100 C. and then at
130-150 C., allow to cool in a desiccator and weigh. Repeat the
heating, etc., until constant weight is obtained (2). Weigh as AgCl.
Notes. 1. For example, from 02 g. of A.R silver nitrate.
2. See last footnote in Section IV, 5.
IV,16. MERCURY
Discussion. Mercury may be estimated in the following forms:
A. Mercuric sulphide, HgS. The precipitation of mercury in hydrochloric
acid solution by hydrogen sulphide as mercuric sulphide is an accurate
procedure in the absence of copper, cadmium, tin, zinc, and thallium; the
latter metals complicate reactions which are based upon the behaviour of
pure mercuric sulphide. Unless the experimental conditions detailed below
are strictly followed, the precipitate is liable to be contaminated with a little
sulphur, which must be removed by extraction with carbon disulphide.
Oxidising agents (nitric acid, chlorine, ferric chloride, etc.) must be absent.
B. Mercury zinc thiocyanate, Hg[Zn(CNS)4]' This method is based upon the
precipitation of mercury from mercuric compounds in neutral or acid
solutions as mercuric zinc thiocyanate with a reagent which contains 39 g. of
ammonium thiocyanate and 29 g. of zinc sulphate per litre. For quantitative
precipitation not more than 5 per cent of free acid should be present in the
solution before the addition of the precipitating agent. If a larger quantity
of acid is present, it must be neutralised with sodium hydroxide solution:
ammonia solution should not be used, because an excessive quantity of
ammonium salts exerts a solvent action upon the precipitate. Cadmium,
cobalt, copper, bismuth, manganese, and mercurous compounds must be
absent, since they give insoluble thiocyanates with the reagent; small
quantities of nickel do not interfere.
C. Copper ethylenediamine mercuri-iodide [Cu en 2 ][HgI4]; ethylenediamine
method. This is a rapid method for the determination of mercury, but
numerous elements interfere.
For further discussion, see Section I, 620.
D. Mercuric para-periodate, Hg 5 (I0 6 }2' Mercury may be determined by
precipitation with sodium periodate as mercuric para-periodate Hg 5 (I0 6 )2 :
moderate amounts of copper, cadmium, aluminium, nickel, zinc, and
magnesium do not interfere, but iron must be absent, as it is precipitated as
ferric periodate. Chlorides and other halides must be absent because they
prevent complete precipitation of mercury. The maximum possible acidity
for complete precipitation is 0'I5N-nitric acid or OIN-sulphuric acid, and
under these conditions a large excess of periodate is required.
424 Quantitative Inorganic Analysis
A. Determination of mercury as sulphide. Procedure. Weigh out
accurately about 015 g. of the mercuric salt (1), dissolve it in 100 ml.
of water, and add a few ml. of dilute hydrochloric acid. Sat'~rate the
cold solution with washed hydrogen sulphide (2), allow the precipitate
to settle, and filter through a weighed Gooch, sintered-glass or porous-
porcelain crucible. Wash the precipitate with cold water (3), and
weigh it, as HgS, after drying at 105-110 C. (4).
Notes. 1. A.R. mercuric chloride is suitable. Alternatively, -the solution
should contain not more than 01 g. of mercuric mercury per 100 ml., and
should be free from oxidising agents.
2. The colour of the mercuric sulphide precipitate will become perfectly
black as soon as the liquid is saturated with the gas.
3. If the presence of sulphur is suspected, the precipitate is washed with
hot water, alcohol, carbon disulphide, or alcohol + ether, and then dried at
l05-ll0 C.
4. A rapid method for weighing the precipitate, collected in a sintered-
glass or porous-porcelain crucible, is as follows. After washing the mercuric
sulphide with cold water, wash it five or six times with rectified spirit, followed
by several times with small volumes of anhydrous ether, and then suck the
precipitate dry on the pump for 10 minutes. Wipe the outside of the
crucible dry with a clean linen cloth and leave in a vacuum desiccator for
10 minutes. Weigh as HgS. .
B. Determination of mercury as mercuric zinc thiocyanate. Pro-
cedure. Weigh out accurately about 02 g. of the mercuric salt (e.g.,
A.R. mercuric chloride) into a 250-ml. beaker, and dissolve it in 100 ml.
of cold water containing 2 drops of concentrated hydrochloric acid.
Add 25 ml. of the ammonium thiocyanate-zinc sulphate reagent (see
Discussion). Stir vigorously with a previously moistened glass rod
for 2-3 minutes, but avoid touching the walls of the beaker. The
initially clear liquid gradually becomes turbid during the stirring, and a
white crystalline precipitate slowly forms. Allow the contents of the
beaker to stand for at least 2 hours. Filter the precipitate on a weighed
sintered-glass or porous-porcelain crucible; transfer the precipitate to
the crucible with the aid of a wash-liquid composed of 5 ml. of the
precipitating reagent and 450 ml. of water. (The precipitate is slightly
soluble in water, but practically insoluble in the special wash-liquid.)
Finally, wash the precipitate five times with the special wash-liquid,
and then once with a little water to remove the adhering wash-liquid.
Dry the crucible and precipitate in an electric oven maintained at 105
2 C. until constant in weight. Weigh as Hg[Zn(CNS)4].
C. Determination of mercury by the ethylenediamine method.
Procedure. The neutral or faintly ammoniacal mercury solution should
occupy a volume of 80-500 mI., and contain not more than about 02 g.
Hg. Treat with excess (say, 2-3 g.) of KI in the form of a 2 per cent
solution, heat nearly to boiling and precipitate with a boiling, concen-
trated aqueous solution of copper ethylenediamine nitrate [Cu en 2] (N0 3 )2
or of the corresponding sulphate (Section I. 620). Allow to cool to
room temperature and filter off the dark blue-violet, crystalline complex
[Cu en2[[HgI4] on a weighed crucible (Gooch, sintered-glass, or porous-
porcelain). Wash three to six times with a solution containing 02 g.
of KI and 02 g. of [Cu en 2] (N0 3 )2,2H 20 (or the corresponding sulphate)
in 200 ml. of water. To remove the water adhering to the wall of thp
crucible, wash three or four times with 2-ml. portions of 95 per cent
Gravimetric Analysis 425
alcohol and finally three or four times with 2-ml. portions of anhydrous
ether. Suck the precipitate dry at the pump for 10 minutes, and dry
the precipitate for 10 minutes (or to constant weight) in a vacuum
desiccator. Weigh as [Cu en 2 [[Hg1 4].
For the determination of mercury in aqua regia solution (up to 03 g.
IIg in 100-200 ml.), render the solution faintly alkaline with ammonia
solution, add a large excess of potassium iodide (say, 3-4 g. K1 in the
form of a 2 per cent solution), heat to boiling and precipitate as above.
When precipitation is complete, dilute-with distilled water (one
quarter of the total volume), aIIow to cool slowly to room temperature,
and complete the determination as already detailed.
D. Determination of mercury as mercuric para-periodate. Procedure.
For practice in this determination, dissolve about 02 g., accurately
weighed, of A.R. mercury in nitric acid of sp. gr. 12, and evaporate the
solution just to dryness. Dissolve in 150 ml. of 0I5N-nitric acid or
oIN-sulphuric acid, heat to boiling, and add slowly and with constant
stirring a solution of 2 g. of sodium or potassium periodate in 50 ml. of
water. Allow to cool, collect the precipitate on a sintered-glass or
porous-porcelain crucible, wash with warm water, and dry at 100 C.
to constant weight. Weigh as Hg 5 (10 6 )2'
The mercury may also be determined volumetrically as follows.
Transfer the precipitate quantitatively (for experimental details, see
Section IV. 32D) to a filter-flask, add a solution of 2-3 g. of pure
potassium iodide in 10-15 ml. of water, and stir until the periodate has
dissolved. Acidify wi~h 10 ml. of 2N-hydrochloric acid, and titrate
the liberated iodine with OIN-sodium thiosulphate, using starch as
indicator. The reaction is :
+
Hg 5 (10 s)2 34K1 + 24HCl . 5K 2[Hg1 4] + 819 + 24KCl +12HzO
IV,17. BISMUTH
Di8CU88iDn.. Bigmllth may be satisfactorjJy determjned jn the foJJowjng
forms:
A. Bismuth oxyiodide, BiOI. The cold bismuth solution, weakly acid with
nitric acid, is treated with an excess of potassium iodide when BiI3 and some
K[BiI4] are formed:
Bi(N0 3)3 + 3KI = BiI3 + 3KN03
BiI3 + KI = K[BiI4]
Upon dilution and boiling, bismuth oxyiodide is formed, and is weighed as
such after suitable drying.
EiI3 + H 2 0 = BiOI + 2HI
(black)
K[BiI4] + H 20 = BiOI + KI + 2HI
(yellow)
A large excess of potassium iodide should be avoided, since the complex
salt is not so readily hydrolysed as the triiodide. This is an excellent
method, because the oxyiodide is precipitated in a form which is very
convenient for filtration and weighing.
B. Bismuth pyrogallate, Bi(C6H303). The precipitation of bismuth with
pyrogallol is quantitative only if the acidity (hydrochloric, sulphuric, or
nitric acid) does not exceed OIN. The method is an excellent one for the
determination of bismuth in the presence of lead, cadmium, and zinc.
Antimony, which form!> a similar complex, must, of course, be absent.
426 Quantitative Inorganic Analysis
C. Bismuth oxide, Bi 20 3, through the cupferron complex. The bismuth in
hydrochloric or nitric acid solution is precipitated as the cupferron complex
(see Section I, 62B), and the latter is converted by ignition into, and weighed
as, Bi 20 3 This procedure separates bismuth from cadmium, lead, arsenic,
mercury, antimonic, and zinc ions.
D. Bismuth "oxinate ", Bi(CgH60N);;. This method uses oxine as the
precipitating agent. For the advantages and limitations of this versatile
reagent, see Section I, 62C. Halogens must be absent, as there is a tendency
for compounds of the general formula (C g H 70N)HBiX4 (where X = halogen)
to be precipitated.
E. Bismuth phosphate, BiP0 4 The precipitation of bismuth as phosphate
is a good method for its determination. Under the correct experimental
conditions a dense crystalline precipitate is obtained, which may be collected
on a porous-porcelain filter-crucible, ignited, and weighed as BiP04 The
procedure serves to separate bismuth from silver, copper, cadmium, mercury,
and the aluminium, zinc, and calcium groups.
F. Metallic bismuth. The electrolytic method for the determination of the
element is described in Section IV, 85.
A. Determination of bismuth as oxyiodide. Procedure. The cold
bismuth nitrate solution, containing 01-015 g. of Bi (1), rp.ust be
slightly acid with nitric acid (2), and occupy a volume of about 20 rol.
Add finely powdered solid potassium iodide, slowly and with stirring,
until the supernatant liquid above the black precipitate of bismuth
tri-iodide is just coloured yellow (due to K[BiI 4]). Dilute to 200 m!:
with boiling water, and boil for a few minutes. The black tri-iodide is
converted into the copper-coloured precipitate of the oxyiodide. The
supernatant liquid should be colourless; if this is yellow, a further 100
ml. of water should be added, and the boiling continued until colourless.
Add a few drops of methyl orange indicator, and then sodium acetate
solution (25 g. per litre) from a burette until the solution is neutral.
Filter off the precipitate through a weighed Gooch, sintered-glass, or
porous-porcelain crucible, wash with hot water, and dry at 105-110 C.
to constant weight. Weigh as BiOI.
Notes. 1. A suitable solution for practice can be obtained by dissolving
about 015 g. of pure bismuth (the A.R. product is obtainable, inter alia,
from the Mallinckrodt Chemical Works, U.S.A.), accurately weighed, in the
minimum volume of I : 4 nitric acid.
2. Chloride and bromide should be absent. If the solution is strongly
acid with nitric acid, it should be evaporated to dryness on the water-bath,
and dissolved in a little dilute nitric acid.
B. Determination of bismuth as pyrogallate. Procedure. The solu-
tion (150 ml.) should be weakly acid with nitric acid and contain 0'1-
02 g. of Bi. Treat the solution with dilute ammonia solution until a
permanent turbidity is obtained; render the solution clear by the
cautious addition of a little dilute nitri{) acid. Heat to boiling, and
add a slight excess of a solution of pure pyrogallol (Section I, 62N)
in air-free water. A yellow, finely crystalline precipitate is immediately
formed. Boil for a short time, test for completeness of precipitation
with a little of the reagent, dilute slightly, and filter through a weighed
sintered-glass or porous-porcelain crucible after the precipitate settles
out. Wash with 0'05N-nitric acid, and finally with water. Dry to
oonstant weight at 105 C. Weigh as Bi(CsH303)'
The following alternative method has been recommended. Add I g.
Gravimetric Analysis 427
of pure pyrogallol to the solution (150 ml.) containing about 01 g. of
Bi and heated to 70 C. Then add 0'5N-ammonium hydroxide solution
dropwise until a distinct turbidity forms. Heat the resulting solution
to boiling, add 2 drops of thymol-blue indicator, and then more of the
a,mmonia solution until the solution is basic. Heat on a water-bath
for 10 minutes, filter on a sintered-glass or porous-porcelain filter-
crucible, wash, and dry to constant weight at 105 C. Weigh as
Bi(CsH 3 0 3 )
C. Determination of bismuth as oxide after precipitation as the cup-
ferron complex. Procedure. Treat the aqueous bismuth nitrate
solution (200 mI.) with freshly prepared 6 per cent aqueous cupferron
solution until there is present at least three times as much cupferron as
bismuth (i.e., .q::03 g. per 01 g. Bi). Heat the solution to boiling,
add ammonia solution until the liquid is alkaline (litmus-paper),
followed by dilute nitric acid until it is just acid. Filter the precipitate
through a quantitative filter-paper, and wash with 01 per cent cup-
ferron solution containing a few drops of dilute nitric acid. Ignite in
a crucible in the usual manner (Section II, 36), and finally with free
access of air over the full flame of a Bunsen burner to constant weight.
Weigh as Bi 20 3
D. Determination of bismuth with" oxine." Procedure. The solu-
tion of bismuth nitrate (100 mI.) should contain sufficient tartaric acid
to prevent precipitation in the following stages. Add a drop or two of
phenolphthalein, and then dilute ammonia solution until the indicator
is just pink. Acidify with acetic acid, and add 1-2 g. of ammonium or
sodium acetate for each 005 g. of Bi expected to be present. Heat to
60-70 C., treat rapidly with a saturated alcoholic solution of oxine
(excess is without influence), then heat almost to boiling, and allow to
cool. Filter off on a weighed sintered-glass or porous-porcelain crucible,
wash with hot water, and dry to constant weight at 130-140 C. Weigh
as Bi(CsH60N)s.
E. Determination of bismuth as phosphate. Procedure. The solution
(100 ml.) may contain up to 01 g. of Bi and should be free from chloride.
Add concentrated ammonia solution until a slight permanent precipitate
is obtained; dissolve this precipitate in 2 ml. of dilute nitric acid (1 : 1).
Heat to boiling and add, whilst stirring constantly, 30 ml. of 10 per
cent diammonium hydrogen phosphate solution from a burette. Dilute
to 400 ml. with boiling water, and allow to stand 10-15 minutes on a
water-bath or hot plate. Decant through a weighed porous-porcelain
filter-crucible and wash the precipitate with 3 per cent ammonium
nitrate solution containing a few drops of nitric acid per litre. Dry
and ignite gently upon a crucible-ignition dish or inside a larger crucible
(Fig. II, 31, 4). Weigh a\ BiP0 4
as [(C13H9N)2H2] (CdI 4)
C. Determination of cadmium as quinaldinate. Procedure. The
solution' (150 ml.) should be neutral or weakly acid with acetic acid,
and should contain 0,1-015 g. of Cd. Heat the solution to boiling,
and remove the source of heat. Add the reagent (a 3 3 per cent solution
of quinaldinic acid or of the sodium salt in water) dropwise with
vigorous stirring until present in slight excess. Then neutralise care-
fully with dilute ammonia solution, and allow the white curdy precipi-
tate to settle. When cold, wash with cold water by decantation, filter
through a sintered-glass or porous-porcelain crucible, wash thoroughly
0
with cold water, and dry at 125 C. to constant weight. Weigh as
Cd(C 1oH 6 0 2N)2' .
D. Determination of cadmiu~ by the pyridine method. Procedure.
The solution (75-100 ml.) should contain about 01 g. of Cd (1) and be
neutral or very feebly acid. Add 05-\"9 g. of A.R. ammonium thio-
cyanate, stir, heat to boiling, and treat ~e solution with 1 m!. of pure
pyridine dropwise and with stirring. The complex slowly separates as
the solution cools. Filter the cold solution through a weighed sintered-
glass or porous-porcelain crucible, transfer the precipitate to the crucible
with the aid of Solution 1. Wash four to five times with Solution 2, then
twice with I-ml. portions of Solution 3, and finally five to six times
with small volumes (ca. 1 ml.) of Solution 4. (For further experimental
details, see under Copper, Section IV, 19E, and Zinc, Section IV, 34D.)
Dry the precipitate in a vacuum desiccator (Fig. 2-10) for 10-15 minutes
and weigh. Repeat the drying until constant weight is attained.
Weigh as [Cd(C 5 H 5N)2](CNS)2'
Solution 1. 100 Ml. of water containing 03 g. of NH4CNS and 05 ml. of
pyridine.
Solution 2. 73MJ. of water, 25 ml. of 95 per cent alcohol, 01 g. ofNH4CNS,
and 2 ml. of pyridine.
Solution 3. 10 Ml. of absolute alcohol and 1 ml. of pyridine.
Solution 4. 15 Ml. of absolute (sodium dried) ether and 2 drops of pyridine.
IV,19. COPPER
Discussion. Copper may be determined in the following forms:
A. Cuprous thiocyanate, Cu 2(CNS)2' This is an excellent method, since
most thiocyanates of the metals are soluble. Separation may thus be
effected from bismuth, cadmium, arsenic, antimony, tin, iron, nickel, cobalt,
manganese, and zinc. The addition of 2-3 g. of tartaric acid is desira"ble for
the prevention of hydrolysis when bismuth, antimony, or tin are pres(jnt.
Excessive amounts of ammonium salts or of the thiocyanate precipitant should
be absent, as should also oxidising agents and high acidity. Lead, mercury,
the precious metals, selenium, and tellurium interfere and contaminate the
precipitate. .
B. Copper benzoinoxime, Cu(C 14H l1 0 2N). IX-Benzoinoxime (cupron) is a
specific reagent for the determination of copper in ammoniacal solutions
(compare Section I, 62D). A green, heavy, and readily filterable precipitate
is obtained: this is insoluble in water, dilute ammonia solution, acetic acid,
tartaric acid, and alcohol, is slightly soluble in concentrated ammonia
solution, and readily soluble in mineral acids. Precipitation is quantitative
in ammoniacal tartrate solutions: separation can thus be effected from iron
and other metals whose hydroxides are not precipitated in tartrate solutions.
Separation can also be made from cadmium, zinc, cobalt, and nickel, which
are not precipitated in ammoniacal solutions.
C. Copper salicylaldoxime, Cu(C 7H 50 2N)2' In this method silver, mercuric,
arsenious, nickel, cobalt, and zinc ions do not interfere provided the solution
contains sufficient acetic acid; the copper complex alone is insoluble in acetic
acid (compare Section I, 62E). Ferric iron is carried down with copper
Gravimetric Analysis 431
salicylaldoxime and interferes seriously. In neutral or in very faintly
acid solution nickel and cobalt are precipitated, but the other ions remain in
solution. An excellent method for the separation of copper and nickel is
thus available (see Section IV, 32B).
D. Copper quinaldinate, Cu(C101isON2)2,H20. Quinaldinic acid or its
sodium salt is a specific reagent for copper if precipitation is made in sul-
phuric acid solution and iron and zinc are absent (compare Section I,
62M). With this reagent, a determination of copper may be completed in
2 hours.
E. [Cu(C 5H 5N)2](CNS)2; pyridine method. If a neutral or faintly acid
copper solution is treated with ammonium thiocyanate and pyridine, di-
pyridine copper dithiocyanate is quantitatively precipitated. This precipi-
tate is collected and washed, inter alia, with alcohol and ether containing a
little pyridine, and then dried simply by leaving in a vacuum desiccator for
10-20 minutes. A determination can be completed in less than 1 hour.
This rapid method is applicable in the absence of cadmium, nickel, cobalt,
zinc, and manganese (see Section I, 62K). Large quantities of ammonium
salts must be absent, as these exert a solvent action upon the precipitate.
If the solution is strongly acid, it must be evaporated to dryness and the
residue dissolved in water.
F. Copper ethylenediamine mercuri-iodide [Cu en 2][HgI4]; ethylenediamine
method. This, like E, is a rapid method for the determination of copper.
Owing to the small conversion factor (007126) the procedure is valuable for
the determination of small amounts of copper.
For further discussion, see Section I, 620.
G. Metallic copper. The electrolytic method is one of the best for the
determination of copper. Comparatively large quantities (up to 5 g.) can
be handled (see-Section IV, 78 for details).
A. Determination of copper as cuprous thiocyanate. Procedure.
Weigh out accurately about 04 g. of the copper salt (1) into a 250-mL
beaker, and dissolve it in 50 mL of water. Add a few drops of dilute
hydrochloric acid, and then a slight excess (2-3 mI.) offreshly prepared
saturated sulphurous acid solution. Dilute the cold liquid to about
150 mL, heat to boiling, and add freshly prepared 10 per cent ammonium
thiocyanate solution, slowly and with constant stirring, from a burette
until present in slight excess. The precipitate of cuprous thiocyanate
should be white; the mother liquor should be colourless and smell of
sulphur dioxide. Allow to stand for several hours, but preferably
overnight. Filter through a weighed filter-crucible (Gooch, sintered-
glass, or porous-porcelain), and wash the precipitate ten to fifteen times
with a cold solution prepared by adding to every 100 mL of water 1
mL of a 10 per cent solution of ammonium thiocyanate and 5-6 drops
of saturated sulphurous acid solution, and finally several times with
20 per cent alcohol to remove ammonium thiocyanate (2). Dry the
precipitate to constant weight at 110-120 C. (3). Weigh as Cu 2 (CNS)2'
Notes. 1. A.R. copper sulphate pentahydrate is suitable for practice in
this determination. 04 Gram of this contains about 01 g. of Cu.
2. Alternatively, but less desirably, the precipitate may be washed with
cold water until the filtrate gives only a slight reddish coloration with ferric
chloride, and finally with 20 per cent alcohol.
3. The precipitate, collected in a sintered-glass or porous-porcelain crucible,
may be weighed more rapidly as follows. Wash the cuprous thiocyanate
five or six times with rectified spirit, followed by a similar treatment with
small volumes of anhydrous ether, then suck the precipitate dry at the pump
432 Quantitative Inorganic Analysis
for 10 minutes, wipe the outside of the crucible with a clean linen cloth and
leave it in a vacuum desiccator for 10 minutes. Weigh as Cu 2 (CNS)2'
B. Determination of copper with a-benzoinoxime. Procedure. Treat
the neutral solution, which should be free from ammonium salts and
contain not more than 0-05 g. of copper, with dilute ammonia solution
until a clear blue solution is obtained. Heat to boiling arid precipitate
the copper by the addition, dropwise, of a 2 per cent alcoholic solution
of the reagent. Precipitation is complete when the blue colour of the
solution disappears. Filter the heavy green precipitate on a weighed
sintered-glass or porous-porcelain crucible, wash with hot 1 per cent
ammonia solution, then with warm alcohol, and finally with hot water.
Dry to constant weight at 105-115 C. Weigh as CU(C14HU02N). It
is recommended that completeness of washing be tested for by washing
the dry precipitate with warm alcohol followed by hot water. Dry
again to constant weight at 105-110 C.
C. Determination of copper with salicylaldoxime. Procedure. Add
2N-sodium hydroxide to the copper solution (100 mI.), contaiI}:'ng
0,05-0,1 g. of Cu, until a slight permanent precipitate is formed, and
dissolve this by the addition of a little dilute acetic acid. * Add the
salicylaldoxime reagent (for preparation, see Section I, 62E) in slight
excess at room temperature. Filter off the precipitated complex on a
weighed sintered-glass or porous-porcelain crucible, wash with water
until the washings give no colour with ferric chloride, and dry to con-
stant weight at 100-105 C. (about 1 hour). Weigh as Cu(C7H 50 2Nh
0
Decomposition occurs above 115 C.
D. Determination of copper as quinaldinate. Procedure. Acidify the
solution (ca. 150 mI.), containing up to 01 g. of copper, with 2-5 ml.
of 2N-sulphuric acid, heat to boiling, and add the reagent (for prepara-
tion, see Section I, 62M) slowly and with stirring until present in slight
excess. The green crystalline precipitate of copper quinaldinate
separates out immediately. Stir the precipitate vigorously and allow
to stand for 5-10 minutes. Wash with hot water by decantation, then
transfer to a weighed sintered-glass or porous-porcelain crucible and
wash with hot water until the excess of the reagent is removed. ]jry at
1l0-1l5 C. to constant weight. Weigh as Cu(C 1o H 6 0 2N)2,H:p.
E. Determination of copper by the pyridine method. Procedure. The
solution (100 ml.) should contain not more than 01 g. of Cu (1) and be
neutral or very faintly acid. Add pure pyridine dropwise until the
colour of the solution is practically azure-blue (1-2 ml. should suffice),
then add 05 g. of solid A.R. ammonium thiocyanate, and stir vigorously.
After a few minutes, collect the precipitate on a weighed sintered-glass
or porous-porcelain crucible; transfer the precipitate to the crucible
with the aid of Solution 1. Wash the precipitate six to eight times
with Solution 2, then wash the walls of the crucible two or three times
with 15-ml. portions of Solution 3 (use a 2-ml. pipette for this purpose),
and finally several times ",ith small volumes (1-2 ml.) of Solution 4.
It is important to suck the precipitate almost dry between each washing;
it is advisable also to stir the precipitate with a thin glass rod during
the washing with Solutions 3 and 4. Dry the crucible and precipitate
in a vacuum desiccator (Fig. II, 10, 4) for 5-20 minutes, according to
its weight. Weigh as [CU(C5H5N)2] (CNS)2' .
* Quantitative precipitation of copper commences at pH 26.
Gravimetric Analysis 433
Solution 1. 100 MI. of water containing 03 g. of NH 4CNS and 03 ml. of
pyridine.
Solution 2. 80 Ml. of 95 per, cent alcohol, 192 ml. of water, 08 ml. of
pyridine, and 005 g. of NH 4CNS.
Solution 3. 10 Ml. of absolute alcohol+ 2 drops of pyridine.
Solution 4. 20 Ml. of absolute (sodium dried) ether+ 2 drops of pyridine.
Note. 1. For practice in this determination, the student may employ ca.
025 g., accurately wejghed, of A.R. copper sulphate.
IV,20. ARSENIC
Discussion. Arsenic may be determined in the following forms:
A. Arsenic trisulphide, AS 2S3 The arsenic must be present in the tervalent
state. Arsenic in the tervalent state (ensured by the addition of, for ex-
ample, ferrous sulphate, cuprous chloride, pyrogallol, or phosphorous acid)
may be separated from other elements by distillation from a hydrochloric
0
acid solution, the temperature of the vapour being held below 108 C.;
arsenic trichloride alone (also germanium chloride, if present) volatilises and
is collected in water or in hydrochloric acid.
B. Magnesium pyroarsenate, Mg 2As 20 7 H{lre the arsenic must be present
in the quinquevalent state (e,g., as arsenate). Phosphates and other sub-
stances which give a precipitate with magnesia mixture must be absent, as
must also organic matter, for this reduces the substance, and arsenic is
volatilised.
C. Ammonium uranyl arsenate, NH 4U0 2As0 4 ,xH 20, and subsequent weighing
as uranous uranate, U30 S' The addition of a uranyl salt solution to an arsenate
solution containing excess of ammonium ions results in the precipitation of
ammonium uranyl arsenate, which is soluble in mineral acids but insoluble in
434 Quantitative Inorganic Analysis /
acetic acid. Upon igniting the precipitate, the arsenic is completely volatil_
ised, leaving a moss-green residue which consists mainly of U 3 0 S : this
residue is dissolved in conceutrated nitric acid, and the resultant uranyl
nitrate upon cautious evaporation and subsequent ignition yields pure black
U 3 0 g , and is weighed in this form.
If the solution contains arsenite, the latter must first be oxidised to arsen-
ate with O'IN-potassium bromate in hydrochloric acid solution at 70 C. in
the usual way (Section Ill, 137). A method is thus available for the deter-
mination of arsenite and arsenate in admixture. The arsenite is first deter-
mined with standard potassium bromate solution, and the total arsenate in
the resulting liquid is then determined by precipitation as the uranium salt.
A. Determination of arsenic as trisulphide. Procedure. Pass a rapid
stream of washed hydrogen sulphide through a solution of the arsenious
arsenic (1) in 9N-hydrochloric acid at 15-20 C. Allow to stand for an
hour or two, and filter through a weighed filter-crucible (Gooch, sin-
tered-glass, or porous-porcelain) (2). Wash the precipitate with
8N-hydrochloric acid saturated with hydrogen sulphide, then succes-
sively with alcohol, carbon disulphide (to remove any free sulphur
which may be present), and alcohol. Dry at 105 C. to constant weight,
and weigh as As 2S 3
Notes. 1. A suitable solution for practice in this estimation is prepared by
dissolving about 03 g. of A.R. arsenious oxide, accurately weighed, in 9N-
hydrochloric acid.
2. Sometimes a film of arsenious sulphide adheres to the glass vessel in
which precipitation was carried out; this can be dissolved in a little ammonia
solution and the sulphide re-precipitated with the acid washing liquor.
B. Determination of arsenic as magnesium pyroarsenate. Procedure.
The solution must contain all the arsenic as arsenate, and have a
volume of not more than 100 ml. per 01 g. of arsenic. Add 5 ml. of
concentrated hydrochloric acid slowly and with constant stirring to the
arsenate solution (100 ml.) (1). Add a few drops of methyl-red indi-
cator, followed by 10-15 ml. of magnesia mixture (2) for each 01 g.
of As present; the magnesia mixture must he added dropwise and with
continuous stirring. Cool the solution in ice water, and add pure con-
centrated ammonia solution slowly and with constant stirring until
the solution is alkaline. Stir the liquid for a few minutes, and add 10
ml. of concentrated ammonia solution. Allow the solution to stand
at room temperature for at least 4 hours, but preferably overnight.
Filter the precipitate through a weighed silica (Vitreosil) or porous-
porcelain filter-crucible, wash with cold 1 : 25 ammonia solution until
free from chloride, and then remove as much as possible of the liquid
by suction. Dry the precipitate at 100 C. for 1-2 hours, place the
crucible inside a nickel crucible (Fig. II, 31, 4), or upon a crucible
ignition dish, and apply heat slowly at first until no more ammonia is
evolved, and finally at the full temperature of a Meker-type burner for
10 minutes (3). Cool in a desiccator and weigh. Repeat the heating,
etc., until constant weight is attained. Weigh as Mg 2As 20 7 (4).
Notes. 1. A suitable solution for practice is prepared by dissolving about
05 g., accurately weighed, of pure sodium arsenate NailHAs04,I2H20 (the
A.R. product is obtainable, inter alia, from the Mallinckrodt Chemical Works,
U.S.A.) in 100 ml. of water.
Gravimetric Analysis 435
2. The magnesia mixture is prepared as follows. Dissolve 25 g. of magnesium
chloride MgCI 2 ,6H 2 0 and 50 g. of ammonium chloride in 250 ml. of water.
Add a slight excess of ammonia solution, allow to stand overnight, and filter
if a precipitate is present. Auidify with dilute hydrochloric acid, add 2 ml.
excess of concentrated hydrochloric acid, and dilute to 500 ml.
3. The best results are obtained by conducting the final ignition in an
electrically heated muffie furnace at 800-900 C.
4. The following procedure permits of the weighing as magnesium ammonium
arsenate MgNH 4As0 4 ,6H 20. Treat the concentrated arsenate solution with
3-5 g. of ammonium chloride and 10-15 ml. of magnesia mixture. Add
hydrochloric acid dropwise until the precipitate which has formed is dissolved.
Add 1 drop of phenolphthalein to the cold solution, stir, then enough 25 per
cent ammonia solution to turn the solution red, followed by an amount of
concentrated ammonia solution equal to one-third of the volume of the
solution. At this stage the total volume of the solution should not exceed
60-70 ml. for each 01 g. of As present. Cool in ice water for 1-2 hours,
filter through a weighed crucible * (sintered-glass or porous-porcelain), wash
with 25 per cent ammonia solution, followed by 95 per cent alcohol (five or
six times), and small volumes of anhydrous ether (five or six times). Dry in a
vacuum desiccator for 10 minutes or to constant weight. Weigh as
MgNH 4As0 4 ,6H 20, which contains 2589 per cent arsenic.
IV,21. ANTIMONY
Discussion. Antimony may be determined in the following forms:
A. Antimony trisulphide, Sb 2S3 This method is of limited application,
since no other elements that are precipitable by hydrogen sulphide in acid
solution can be present, and the sulphide must be dried and finally heated
in an atmosphere of carbon dioxide at 280-330 C. Arsenic can be separated
by removal by distillation as arsenic trichloride; tin can be removed by
precipitation in the presence of oxalic and tartaric acids or of phosphoric
acid.
B. Antimony tetroxide, Sb 20 4 Instead of weighing the antimony as the
trisulphide after the procedure described in Method A, the wet sulphide (or
sulphide dried at 100 C.) may be converted by controlled oxidation with
fuming nitric acid into the higher oxide, and subsequently heated at 820-
850 C., and weighed as Sb 2 0 4 Since this process is an inconvenient one and
the oxide is very easily reduced, it will not be described in detail.
* Wash the crucible several times with alcohol (95 per cent), followed by anhydrous
ether, wipe the outside, leave in a vacuum desiccator for 5 minutes and weigh.
436 Quantitative Inorganic Analysis
C. Antimony pyrogallate, Sb(C sH 50 3 ). Antimonious salts in th~ presence .
of tartrate ions may be quantitatively precipitated with a large' excess of
aqueous pyrogallol as the dense antimony pyrogallate. The method allows
of a simple separation from arsenic; the latter element may be determined
in the filtrate from the precipitation of antimony by direct treatment with
hydrogen sulphide.
The volumetric methods described in Chapter III are simpler, quite as
accurate, and more rapid; they are therefore to be preferred.
; IV,22. TIN
~ Discussion. Tin may be determined in any of the following ways:
i A. Tin dioxide, Sn0 2 The method depends upon the oxidation of the tin
to the quadrivalent state, precipitation with ammonium hydroxide, followed
by ignition to stannic oxide, Sn0 2 This procedure is satisfactory when
applied to solutions containing tin alone, but it cannot be used directly in
the presence of many other elements.
Tin is, however, frequently estimated as the dioxide in alloys (e.g., in brass
or gun-metal). The alloy is treated with nitric acid, when a precipitate of
hydrous stannic oxide is formed; the formula for this may be written, for
simplicity, as H 2SnOa, meta stannic acid:
3Sn + H 20 + 4HN0 3 = 3H 2Sn03 + 4NO
The precipitate possesses colloidal character and exhibits powerful adsorption
properties for certain ions, for example, iron, lead, copper, nickel, and zinc.
It is advisable to use macerated filter-paper in the subsequent filtration and
also to wash the precipitate with dilute nitric acid in order to avoid peptisa-
tion. The precipitate is ignited at the highest temperature of a Meker-
type burner to stannic oxide:
H 2SnOa = Sn0 2 + H 20
Owing to the ready reduction of the oxide to the metal, the carbon of the
filter-paper must be burnt off at as Iowa temperature as possible and the
flame gases excluded from the crucible.
The precipitate should be white, but rarely is because of the presence of
impurities. The amount of impurity may be determined by adding to the
impure weighed oxide fifteen times its weight of pure ammonium iodide and
heating for 15 minutes in an electric oven at 425-475 C., or until no further
fumes are evolved. The tin is volatilised quantitatively as stannic iodide:
Sn0 2 + 4NH41 = SnI4 + 4NHa + 2H 20
The residue is treated with 2-3 ml. of concentrated nitric acid, cautiously
evaporated, ignited, and the residual metallic oxides weighed; the loss in
weight gives the weight of pure stannic oxide present in the precipitate.
The treatment with nitric acid is necessary, for the other metals are converted
into iodides and/or oxyiodides, which are only slowly converted into the
oxides by heating in air.
B. Precipitation with cupferron and weighing as stannic oxide, Sn02 This
process permits of the precipitation of tin in the presence of aluminium,
chromium, cobalt, nickel, and manganese. In the presence of 5 ml. of 48 per
cent hydrofluoric acid per 200-400 ml. of solution which is 05N in acid, tin
is not precipitated by hydrogen sulphide, whereas copper, lead, tervalent
arsenic, and antimony are thus precipitated; many separations are
therefore possible by this method. The addition of several grams of tartaric
acid and of sodium acetate is desirable if antimony is present.
C. Precipitation with phenylarsonic acid and weighing as stannic oxide, Sn0 2
This method is applicable in the presence of zinc, copper, and other
elements commonly associated with tin in alloys, etc. (compare Section I, 62J).
Zirconium and thorium seriously interfere and must be absent.
The volumetric methods described in Chapter III are more rapid and
equally accurate; they are therefore generally preferred.
IV,23. MOLYBDENUM
Discussion. Molybdenum may be determined in the following forms:
A. Lead molybdate, PbMo0 4 Precipitation as lead molybdate is usually
made by the slow addition of a solution of lead acetate to a hot, dilute
acetic acid-ammonium acetate solution containing the molybdenum. The
method is applicable in the presence of copper, mercury, cobalt, nickel,
manganese, zinc, and magnesium. Alkali salts are not objectionable except
sulphates, which must be absent when the alkaline earths are present. A
great excess of the precipitant should be avoided if chlorides are present.
Free mineral acids prevent complete precipitation, and elements such as iron,
chromium, vanadium, tungsten, silicon, tin, and titanium interfere.
B. Precipitation with cx-benzoinoxime and weighing as molybdic oxide, MoO a
Precipitation as the cx-benzoinoxime complex is made by the addition of
excess of an alcoholic solution of the reagent to a solution of the molyb-
denum compound containing 5 per cent by volume of sulphuric acid. The
precipitate cannot be weighed as such, but must be ignited to molybdic
oxide. The only other elements that give precipitates in mineral acid
solution with the reagent are tungsten, palladium, sexivalent chromium,
quinquevalent vanadium, and tantalum. Chromium and vanadium do not
interfere if they are reduced to the tervalent and quadrivalent states re-
spectively with sulphurous acid. Tungsten may be determined in the
ignited precipitate by extracting with the minimum volume of warm 1 : 3
ammonia solution, filtering, acidifying the ammoniacal solution with hydro-
chloric acid, and then adding a little cinchonine solution; the solution is
allowed to stand overnight, the precipitate filtered off, washed, ignited at
525 0 C., and weighed. The weight of tungstic oxide is deducted from that of
the molybdic oxide.
C. Molybdenum "oxiDate", Mo0 2 (C 9H sON)2' Molybdates yield sparingly
soluble orange-yellow molybdyl "oxinate" with oxine solution; the pH of the
solution should be between the limits 33-76. The complex differs from
other" oxinates " in being insoluble in organic solvents and in many con-
centrated inorganic acids. The freshly precipitated compound dissolves only
in concentrated sulphuric acid and in hot solutions of caustic alkalis. This
determination is of particular interest, as it allows a complete separation of
molybdenum and rhenium.
For the volumetric determination of molybdenum, the precipitate is brought
into solution by repeated digestion with 2-4N-sodium hydroxide solution,
the alkaline solution is slowly introduced with constant stirring into 25-50
ml. of concentrated hydrochloric acid, the solution diluted to 50-100 mI., and
440 Quantitative Inorganic Analysis
then titrated with standard OIN-potassium bromate (Section m, 138;
Procedure A).
1 ml. N-KBr0 3 == 001199 g. Mo
A. Determination of molybdenum as lead molybdate. Procedure.
Weigh out accurately about 04 g. of ferro-molybdenum (I), dissolve it
in 10 ml. of concentrated hydrochloric acid and 2 ml. of concentrated
nitric acid, evaporate to 2-3 mI., dilute to 50 mI., and transfer to a
separating-funnel. Dissolve 5 g. of sodium hydroxide in 200 ml. <?f
water in the original beaker, heat to boiling, and run in the solution
from the separating funnel dropwise and with constant stirring. Rinse
out the funnel twice with boiling water, and add the washings to the
main filtrate. Filter off the precipitated ferric hydroxide and wash with
hot water. Dissolve the precipitate in the minimum volume of dilute
hydrochloric acid, and re-precipitate by slowly pouring into a solution
of about 4 g. of sodium hydroxide in 100 ml. of water. Filter off the
precipitate, wash with hot water, and add the filtrate and washings to
the main filtrate. Acidify with acetic acid, add 50 ml. of a 50 per cent
solution of ammonium acetate, and make up to 500 ml. in a measuring-
. flask. Remove 250 ml. of the solution (2), heat to boiling, and maintain
near the boiling point with a small flame; add from a burette a solution
of lead acetate (containing 4 g. of the salt and I ml. of glacial acetic
acid per 100 ml.) dropwise and with constant stirring. When a slight
excess of the precipitant has been added, the milky solution clears
appreciably. When this occurs, boil for 2-3 minutes whilst the solution -
is stirred, allow to settle, and add a few drops of the reagent to see if
precipitation is complete. A large excess of precipitant should be
avoided. Digest on the steam-bath for 15-30 minutes. Decant the
clear solution through a weighed Gooch or porous-porcelain crucible,
wash by decantation three or four times with 75-ml. portions of hot
2-3 per cent ammonium nitrate solution, transfer the precipitate to
the filter, and wash until the soluble salts have been removed. Dry
and ignite the precipitate at a dull red heat (ca. 600 0 C.) as described
in Section IV. 140. Weigh as PbMo0 4
Notes. 1. The Bureau of Analysed Samples "Ferro-Molybdenum, No.
231 " (a British Chemical Standard) is suitable.
2. If molybdenum is being determined in a simple salt, e.g., in A.R.
molybdic acid or molybdic anhydride, commence at this point. The solution
should contain about 01 g. of Mo in 200 ml. and may be prepared as follows.
Dissolve 015 g., accurately weighed, of A.R. molybdic acid or anhydride, in
50 ml. of dilute ammonia solution, acidify with acetic acid, add 25 ml. of a
50 per cent solution of ammonium acetate, and dilute to 200 ml.
B. Determination of molybdenum with a-benzoinoxime (cupron).
Procedure. Prepare a solution containing 10 ml. of concentrated
sulphuric acid in a volume of 200 ml. and not more than 015 g. of
hexavalent molybdenum. If vanadates or chromates are present, add
sufficient freshly prepared sulphurous acid to reduce them, and heat
to boiling: continue the boiling until the odour of sulphur dioxide can
no longer be detected. Cool to 5-10 C., stir, and slowly add 10 ml. of
a solution of the reagent (2 g. of ex-benzoinoxime in 100 ml. of alcohol)
and 5 ml. extra for each 001 g. of Mo present (from two to five times
the theoretical amount is required). Continue the stirring, add just
sufficient bromine water to tint the solution a pale yellow, and then add
Gravimetric Analysis 441
4-5 mI. more of the reagent. Allow the mixture to stand for 10-15
:minutes at 10-15 C. with occasional stirring, and filter through a
Whatman No. 40 or 640 filter-paper. Wash the precipitate with 200
:ml. of a cold, freshly prepared wash solution (containing 10 mI. of the
reagent, and 2 mI. of concentrated sulphuric acid diluted to 200 mI.).
Transfer the paper_~Llld washed precipitate to a weighed platinum
crucible, char the paI)er at a low temperature without inflaming, and
then ignite to constant weight at 500-525 C. Weigh as Mo0 3 .
As an additional .check, or if contamination of the precipitate is
suspected, treat the ignited residue with 5 ml. of concentrated ammonia
solution, digest, and filter through a small quantitative filter-paper.
Wash well with dilute ammonia solution (I : 99). Ignite the filter-
paper and contents in the original crucible, allow to cool and weigh.
The difference in weight represents the Mo0 3 present.
C. Determination of molybdenum with oxine. Procedure. Neutralise
the solution of alkali molybdate, containing up to 01 g. of Mo, to
:methyl red, and then acidify with a few drops of 2N-sulphuric acid.
Add 5 ml. of 2N-amn10nium acetate, dilute to 50-100 ml., and heat to
boiling. Precipitate th~ molybdenum by the addition of 3 per cent
solution of oxine in dilute acetic acid (for preparation, see Section IV,
37B; Note 2) until the supernatant liquid becomes perceptibly yellow.
Boil gently and stir for 3 minutes, filter through a filter-crucible
(sintered glass or porous porcelain), wash with hot water until free from
the reagent, and dry to constant weight at 130-140 C. Weigh as
Mo0 2(C 9H 6 0N)2
Filter off the bi'aci'c selenium through a weiglrcd filter-crucible, wash with
water, then with alcohol, and qry to' constant w(~ight at 110 0 C. Deter-
mine the tellurium in the filtrate exactly as detailed in B, Procedure A.
IV,25. PLATINUM
Discussion. Platinum may be determined in either of the following forms:
A. Metallic platinum. The platinum solution is treated with formic acid,
best at pH 6, and the precipitated platinum weighed.
B. Ammonium chloroplatinate, (NH 4 MPtcl 6], and subsequent weighing as
platinum. If platinum alone is present in hydrochloric acid solution, it may
be precipitated as ammonium chloroplatinate by the addition of a half-
saturated solution of ammonium chloride, washed, carefully ignited, and
weighed as Pt,
A. Determination as metallic platinum. Procedure. In this estima-
tion any excess af nitric and/or hydrochloric acid present must be
removed. Evaporate the solution of platinulU, containing no other
platinum metals (ruthenium, rhodium, palladium, osmium, and
iridium) and gold, to a syrup on the steam-bath so as to remove 'as
much hydrochloric acid as possible. If nitric a(;id was present, dissolve
the residue in 5 mi. of water, heat on the water-bath for a few minutes,
add 5 ml. of concentrated hydrochloric acid, and again evaporate to a
syrupy consistency. Dissolve the residue in water, and dilute so that
the solution does not contain more than 05 g. ofPt in 100 mi. For each
100 mi. of solution, add 3 g. of anhydrous sodium acetate and 1 mi. of
formic acid. Heat on the boiling water-bath for several hours. Filter
through a quantitative filter-papBr. Add a little more sodium acetate
and formic acid to the filtrate and digest in Ol'der to ensure complete
precipitation. Wash the precipitate with water until free from chloride,
dry and ignite the filter-paper in cant act with the precipitate (Section
II, 36A) to constant weight. Weigh as metalli() Pt.
B. Determination of platinum by precipitation as ammonium chloro-
platinate. Procedure. Only hydrochloric acid may be present in this
444 Quantitative Inorganic Analysis
estimation. The solution should be free from gold (which may be
removed by the cautious addition of sulphurous acid to the solution or
of hydro quinone to the solution 1 2N with respect to hydrochloric acid)
and the other platinum metals (see, however, below). If nitric acid
is present, it must be removed by several evaporations with concen-
trated hydrochloric acid. Dissolve the residue in 5 m!. of concentrated
hydrochloric acid and 20 m!. of hot water, and then add gradually an
equal bulk of half-saturated ammonium chloride solution. Allow to
stand for some hours, or overnight. Filter off the precipitate, wash it
with the ammonium chloride solution, and finally twice with cold water.
Transfer the filter-paper and precipitate to a Main-Smith crucible
(Section II, 36B), heat extremely slowly at first (otherwise loss may
occur), and ultimately raise to a bright red heat. Heat to constant
weight and weigh as Pt.
If other metals of the platinum group are present, the above procedure
does not give satisfactory results. It is necessary to proceed as follows.
Rinse back the precipitate of ammonium chloroplatinate into the precipitat-
ing-vessel, and wash the filter thoroughly with hot water. Slightly acidify
the liquid (150 ml. for 1 g. of Pt) with hydrochloric acid, boil vigorously and
keep stirred by means of a glass tube through which a brisk current of chlorine
is passed (the operation must be performed in the fume chamber). When
the precipitate has dissolved (after a few minutes), stop the current of chlorine
and wash the tube with hot water. The solution now contains chloroplatinie
acid. Then add just enough ammonium chloride solution to combine with the
platinum (6 ml. of a 10 per cent solution for 1 g. of platinum), and evaporate
(hot-plate) to 20 ml. Allow to cool, and dilute with an equal bulk of satur-
ated ammonium chloride solution. After a few hours, filter off the coarsely
crystalline precipitate, wash with half-saturated ammonium chloride solution,
then with a little cold water, ignite cautiously, and weigh as Pt.
IV,26. PALLADIUM
Discussion. Palladium may be determined in one of the folloWing forms:
A. Palladous cyanide, Pd(CN)2' and subsequent weighing as the metal. This
is quite a good method, particularly when large quantities of palladium are
involved, because of the comparative compactness of the precipitate.
B. Palladium dimethylglyoxime, Pd(C 4H 70 2N2b This is one of the best
methods for the estimation of the element. Gold must be absent, for it
precipitates as the metal even from cold solutions. The other platinum
metals do not, in general, interfere. Moderate amounts of platinum cause
little contamination of the precipitate, but with large amounts a second
precipitation is desirable. The precipitate is decomposed by digestion on
the water-bath with a little aqua regia, and diluted with an equal volume of
water; the resulting solution is largely diluted with water, and the palladium
re-precipitated with dimethylglyoxime.
An objection to the precipitation of palladium with dimethylglyoxime is
the voluminous character of the precipitate. Hence if much palladium is
present, an aliquot part of the solution should be used, or the palladous
cyanide method applied. .
C. Palladium 1: 2-cyclohexanedione dioxime, Pd(C sH 90 2N2)2' 1: 2-cyclo-
Hexanedione dioxime (nioxime) yields a highly insoluble yellow compound,
Pd(C sH 90 2N 2)2' with palladium salts at pH values between 1 and 5; it can
be filtered from the hot solution after a brief digestion period. The reagent,
unlike dimethylglyoxime, is soluble in water, and hence the palladium
precipitate is unlikely to be contaminated with excess of reagent. The pre-.
Gravimetric Analysis 445
cipitate is rather bulky, so that determinations are conducted with quantities
not exceeding 20-30 lPg. Common anions do not interfere, nor do beryllium,
aluminium, lanthanum, uranium (VI), and the alkaline-earth ions. Amounts
of platinum (up to that of the palladium) do not interfere; aurous ion at
60 0 C. is partially reduced to metallic gold.
It may be mentioned that palladium may also be precipitated with 0(-
nitroso-f1-naphthol (brown precipitate: subsequently ignited to and weighed
as the metal) or with salicylaldoxime (the precipitate, after drying at llO C.,
is weighed as Pd(C 7H s0 2N)2)' Both procedures may be used for separating
palladium from platinum.
A. Determination of palladium as palladous cyanide. Procedure.
This estimation must be carried out in a fume cupboard provided with
a good draughn.... Nearly neutralise the solution containing up to
03 g. of Pd with sodium carbonate, and add an excess of mercuric
cyanide solution. Heat on the water-bath until the odour of hydro-
cyanic acid has disappeared, and allow the light-yellow precipitate to
settle. Filter the. precipitate through a quantitative filter-paper.
Wash the precipitate first by decantation and then on the filter with
cold water. Dry and ignite in a weighed crucible to constant weight,
using the full heat of a Meker type of burner. Weigh as Pd.
B. Determination of palladium with dimethylglyoxime. Procedure.
The solution should contain not more than 01 g. of Pd in 250 mI., be
025N with respect to hydrochloric or nitric acid, and be free from nickel
and gold. Add, at room temperature, a 1 per cent solution of dimethyl-
glyoxime in 95 per cent alcohol. Use 2-5 ml. of the reagent for every
10 mg. of palladium .. Allow the solution to stand for 1 hour, and then
filter through a weighed filter-crucible (Gooch, sintered-glass, or porous-
porcelain). Test the filtrate with a little of the reagent to make sure
that precipitation is complete. Wash the orange-yellow precipitate
of palladium dimethylglyoxime thoroughly, first with cold water and
then with hot water. Dry at 1l0 C. to constant weight. Weigh as
Pd(C 4 H 7 0 2N 2 )2' J
C. Determination of palladium with 1 : 2-cyclohexanedione dioxime.
Procedure. The solution (volume about 200 mI.) may contain 5-30 mg.
of palladium: the pH may vary from 1 to 5. Heat the solution to
60 C., add slowly from a graduated pipette with stirring 050 inl. of a
08 per cent aqueous solution of nioxime (1) for each milligram of Pd
present. Digest the solution with occasional stirring for 30 minutes
at 60 C., filter through a sintered-glass or porous-porcelain crucible,
and wash well with hot water. Dry at 1l0 C. to constant weight, and
weigh as Pd(C 6 H 9 0 2N 2)2'
Note. 1. The preparation of 1 : 2-cyclohexanedione dioxime is described
in the author's Text Book of Practical Organic Chemistry (including Qualita-
tive Organic Analysis), Second Edition, 1951 (Longmans, Green).
IV,27. GOLD
Discussion. Gold is nearly always determined as the metal. The reducing
agents generally employed are sulphur dioxide, oxalic acid, and ferrous
SUlphate. No free nitric acid must be present in the solution; if this is
the case, the nitric acid must be removed by repeated evaporation with
concentrated hydrochloric acid, and the solution diluted with water. With
sulphurous acid, small amounts of the platinum metals (particularly platinum)
446 Quantitative Inorganic Analysis
may be carried down with the precipitate. It is therefore usually necessary
to re-dissolve the solid in dilute aqua regia and to re-precipitate the gold;
oxalic acid gives a better separation from the platinum metals in the second
precipitation, although the precipitate is somewhat finely divided. Ferrous
sulphate gives satisfactory results for gold alone, but difficulties are introduced
if the platinum metals are subsequently to be determined. Oxalic acid is
slow in its action, and yields a precipitate which is difficult to filter.
The best results are obtained with hydroquinone as the reducing agent.
Precipitation in hot 12N-hydrochloric acid solution is rapid, the gold is
readily filtered, and occlusion of the platinum metals is negligible. Pre-
cipitation in the cold is complete in 2 hours. Palladium in the filtrate can
be precipitated directly with dimethyl-glyoxime, whilst platinum in the
filtrate may be determined either by evaporating to dryness in order to
destroy organic matter and then digesting with a little aqua regia or by
reduction with sodium formate and formic acid.
Gold may also be separated from hydrochloric acid solutions of the,
platinum metals by extraction with ether or with ethyl acetate (compare
Section I, 71); except in special cases these methods do not offer any special
advantages over the reduction to the metal.
Determination of gold as the metal. Procedure A. The solution
should contain not more than 5 ml. of concentrated hydrochloric acid
per 100 mI. of solution, not more than 05-1 g. of Au, and be free from
lead, selenium, tellurium, and the alkaline earths. Add 25 ml. of a
freshly prepared saturated sulp'hur dioxide solution, and digest for 1
hour on the steam-bath in ord'er to coagulate the precipitate. Add
5-10 ml. more of the sulphur dioxide solution, and allow to cool., If
the cold solution smells strongly of sulphur dioxide, the precipitation
of gold is complete. Some of the metal is finely divided, and it is
therefore advisable to treat the filter-paper with a suspension of
macerated filter-paper prepared from a Whatman accelerator or ashless
tablet. Pour the supernatant liquid through a Whatman No. 42 or
542 filter-paper, preferably containing some filter-paper pulp, and
transfer as little as possible of the precipitate to the paper unless one
precipitation is thought sufficient; this will only be the case if very
small amounts of platinum or palladium are present. Wash well by'
decantation with hot dilute hydrochloric acid (1 : 99). Transfer the
filter to the beaker, and re-dissolve the gold in dilute aqua regia; use
8 ml. of concentrated hydrochloric acid, 2 ml. of concentrated nitric
acid, and 10 ml. of water for each gram or less of gold. Filter from the
paper-pulp, and wash thoroughly with hot dilute hydrochloric acid
(1 : 99). Evaporate the filtrate to dryness on the water-bath, add
2-3 ml. of concentrated hydrochloric acid, and evaporate to dryness
again; repeat this operation twice in order to eliminate all the nitric
acid. Treat the residue with 3 ml. of concentrated hydrochloric acid,
5 drops of concentrated sulphuric acid, and 75 ml. of water, disregard
the small amount of gold which may separate, add 25 ml. of a saturated
solution of oxalic acid, and boil for a minute or two. If no further
visible precipitation of gold occurs, digest the solution on the water-
bath for at least 4 hours. Filter off the gold through a filter-paper (as
described above), and wipe the inside of the beaker with small pieces of
quantitative filter-paper to ensure that all the metal is transferred from
the beaker; wash well with 1: 99 hydrochloric acid. Transfer the
filter to a weighed porcelain or silica crucible, burn off the paper care-
fully, and ignite to constant weight. Weigh as Au.
Gravimetric Analysis 447
Procedure B. Treat the dilute solution of the gold, containing only
a little free hydrochloric acid, with a large excess of a clear ferrous
sulphate solution, cover the beaker, and heat on the water-bath for
several hours. Filter off-the precipitated gold through a filter-paper,
and complete the estimation as under Procedure A.
Procedure C. The solution must be free from nitric acid, be about
12N with respect to hydrochloric acid (ca. 5 ml. of concentrated hydro-
chloric acid in 50 ml. of water), and contain up to 02 g. of Au in 50
Illl. Heat the solution to boiling, add excess of 5 per cent aqueous
hydro quinone solution (3 ml. for every 25 mg. of Au), and boil for 20
minutes. Allow to cool, and filter either through a weighed porous-
porcelain crucible or through a Whatman No. 42 or 542 filter-paper
(Section II, 28); wash thoroughly with hot water. The small particles
of gold remaining in the bottom of the beaker (easily seen with a small
flash lamp) are best removed with pieces of ashless filter-paper. Ignite
the porous-porcelain crucible to constant weight. If filter-paper is
used, transfer to a weighed porcelain or silica crucible, and complete
tte estimation as described in Procedure A.
IV,28. ALUMINIUM
Discussion. Aluminium may be determined in the following forms:
A. Aluminium oxide, Al Z0 3 Full details of this determination (precipita-
tion with ammonia solution) are given in Section IV, 9. A more readily
filterable precipitate may be obtained by precipitation in weakly acid solution
with a mixture of equal volumes of a 25 per cent aqueous solution of potassium
iodide and a saturated solution of potassium iodate. The mixture removes
the acid produced by hydrolysis, and causes the reaction to proceed from
left to right:
2AIC13 +
6H 20 ~ 2Al(OHh + 6HCl . (1)
6HCl + KI03 +
5KI = 3H20 + 31 2 + 6KCl
The weakly acid solution (200-300 ml. containing up to 02 g. of AI) is treated
with e.a excess of the KI-KI03 mixture; iodine separates immediately.
After 10 minutes the iodine is removed by the addition of sodium thiosulphate
solution with stirring from a burette, and several ml. excess of the thio-
sulphate solution are added. The mixture is heated on a water-bath for 45
minutes with frequent stirring. The hydrated aluminium oxide is filtered
off, washed with hot water or with 2 per cent ammonium nitrate solution,
ignited, and weighed. The method may be applied also to the precipitation
of chromium and iron as hydroxides from dilute, weakly acid solutions of their
tervalent salts.
Sodium thiosulphate may also be employed to remove the acid formed by
hydrolysis of the aluminium salt (equation (1)) :
6HCl + 3Na S 0
2 2 3 = 3H zO + 6NaCl + 3S + 3S0 2
.,
sulphur dioxide is no longer perceptible. Use 5-10 ml. of this solution in 100 m!. of hot
water.
Gravimetric Analysis 449
manganese, calcium, and magnesium, provided that the amounts of these
elements do not exceed that of the aluminium: for larger quantities, double
precipitation is recommended.
D. Aluminium 8-hydroxy-quinolate, AI(CJl60Nla. Details of this method
are given in Section III, 138A. This procedure separates aluminium from
beryllium (see, however, Section IV, 29), the alkaline earths, magnesium, and
phosphate. For the gravimetric determination a 2 or 5 per cent solution
of oxine in 2N-acetic acid may be used; 1 mI. of the latter solution is
sufficient to precipitate 0003 g. of AI. For practice in this determination,
about 04 g. of A.R. ammonium alum, accurately weighed, may be used.
This is dissolved in 100 mI. of water, The precipitated aluminium" oxinate "
is collected on a weighed filter-crucible (Gooch, sintered-glass, or porous-
porcelain), well washed with cold water, dried to constant weight at
130-140 C., and weighed as AI(C9H60N)a.
B. Determination of aluminium as the basic succinate and ignition
to aluminium oxide. Procedure. The solution should contain about
01 g. of Al and be acid with hydrochloric acid. Add dilute ammonia
.solution until the solution becomes slightly turbid, remove the turbidity
with dilute hydrochloric acid, and add 1-2 drops in excess. Add a
solution of 5 g. of A.R. succinic acid in 100 ml. of water, followed by
10 g. of ammonium chloride and 4 g. of urea; dilute to 500 ml. with
distilled water. Heat the solution to boiling and continue the boiling
for 2 hours after the solution has become turbid (ca. 45 minutes). *
Allow the precipitate to settle for a few minutes, add a Whatman
"accelerator," filter, and wash ten times with a 1 per cent succinic
acid solution made neutral to-.methyl red with ammonia solution. If
any precipitate adheres to the sides of the beaker, dissolve it in a little
dilute hydrochloric acid, add a drop of methyl red or phenol red indi-
cator, and then dilute ammonia solution until just alkaline; filter off
the precipitate of aluminium hydroxide on a separate small filter-paper,
and wash it with a 2 per cent solution of ammonium nitrate. Place
both papers and precipitates in a silica or, preferably, a platinum
crucible, and ignite to constant weight at 1200 C. (compare Section
IV, 9). Weigh as A1 20 3
C. Determination of aluminium as the basic benzoate and subsequent
ignition to the oxide. Procedure. To the slightly acid solution (usually
with hydrochloric acid) containing about 01 g. of Al in a volume of
259-300 mI., add 1 g. of ammonium chloride, 20 mI. of 10 per cent
ammonium acetate solution, 20 mI. of 10 per cent ammonium benzoate
solution, and a few drops of bromophenol-blue indicator. Heat to
80 0 C., add sufficient dilute hydrochloric acid to dissolve any precipi-
tated aluminium benzoate (any benzoic acid which separates out in the
cold will dissolve during the heating) and introduce dilute ammonia
solution from a burette, slowly and with shaking, until the indicator
just commences to change colour and precipitation just begins. Boil
the solution for 1-2 minutes, whereupon further precipitation takes
place and a granular precipitate is formed. Usually at this point the
solution becomes faintly acid again: continue the addition of dilute
ammonia solution from a burette until the indicator acquires the red-
blue colour characteristic of pH 35-4. Boil the solution gently for
* The boiling period (after the appearance of a turbidity) may be reduced to 1 hour
by first partially neutralising the hot solution to bromo-phenol blue or to methyl orange
by the drop-wise addition of dilute ammonia solution: a very. faint opalescence will
appear.
Q
450 Quantitative Inorganic Analysis
2-3 minutes, and digest on a water-bath for 30 minutes, by which
time the precipitate will have settled out. Filter through a quantita-
tive filter-paper, and wash ten times with a hot wash liquor containing
10 g. of ammonium benzoate and 20 ml. of glacial acetic acid per 100
m!. (pH ca. 38). Ignite to constant weight as under B, and weigh as
A1 2 0 3
1V,29. BERYLLIUM
Discussion. Until about 1927 beryllium was nearly always determined
by precipitation as the hydroxide Be(OH)2 with ammonia solution in the
presence of ammonium chloride or nitrate, and subsequently weighing as
the oxide BeO. The method was not entirely satisfactory owing to the
gelatinous nature of the precipitate, its tendency to adhere to the sides of
the vessel, and its liability to adsorption and related effects. Beryllium
hydroxide was usually separated with aluminium hydroxide, which it
resembles in many respects; two methods for the separation of beryllium
and aluminium are given below.
It has been shown (L. Moser, 1927) that the hydroxide may be obtained in
an easily filterable and compact form by precipitation from neut1l6lJ solutions
by heating with ammonium nitrite and methyl alcohol at 70 C., a current
of air being passed through the solution. This method provides a separation
from all metals of the later analytical groups, excepting barium, which should
previously be removed as sulphate; cadmium and thallium also do not
interfere.
Beryllium may also be conveniently estimated by precipitation with
tannin in ammoniacal solution. Elements such as aluminium, chromium,
ferric iron, thorium, zirconium, aQd titanium are precipitated by tannin
from acetic acid solution; beryllium is not precipitated under these
conditions, hence a good method of separation from these elements is avail-
able. If ferric iron is present, slight reduction to the ferrous state occurs;
this is prevented by the addition of a few drops of 10-volume hydrogen
peroxide solution prior to precipitation with tannin.
Beryllium may be quantitatively separated from aluminium (and also
from iron) by means of oxine. An acetic acid solution containing ammonium
acetate is used; the aluminium and iron are precipitated as oxinates, and
the beryllium in the filtrate is then precipitated with ammonia solution.
It has been stated (Stevens and Carron, 1946) that the oxine method of
separation from aluminium and from iron leads to small losses of beryllium.
Excellent results are obtained by first removing the iron by the cupferron
method, destroying the excess of cupferron, and precipitating the beryllium
and aluminium phosphates with ammonium phosphate solution at pH of'
about 62 (methyl-red indicator). The mixed phosphates, unlike the oxides,
are readily decomposed upon fusion with anhydrous sodium carbonate in a
platinum crucible: upon digesting the product with water and allowing to ~
stand overnight, the hydrated beryllia remains quantitatively in the residue,
whilst the alumina (also phosphoric oxide and silica) remain in solution as
the sodium salts. The beryllia is filtered off, washed, ignited, and weighed
as BeO.
In all these methods the element is weighed as beryllia, which is somewhat
hygroscopic. The ignited residue must be cooled in a desiccator over con-
centrated sulphuric acid or phosphorus pentoxide, preferably in a tared and.
stoppered weighing-bottle, and weighed as quickly as possible-usually after
25 minutes.
A. Determination of beryllium by precipitation with ammonia solu-
tion. Procedure. The beryllium solution (200 mI.), prepared with
Gravimetric Analysis 451
nitric acid or hydrochloric acid and containing about 01 g. of Be, must
be almost neutral and contain no other substance pr.ecipitable by
ammonia solution. Heat to boiling, and add dilute ammonia solution
slowly and with constant stirring until present in very slight excess.
Add a Whatman accelerator or one-half of a Whatman ashless tablet,
boil for 1 or 2 minutes, and filter on a vVhatman No. 41 or 541
filter-paper. Transfer as much of the precipitate as possible by rinsing
with hot 2 per cent arp.monium nitrate solution. Remove any pre-
cipitate adhering to the walls of the beaker by dissolving in the mini-
mum volume of hot very dilute nitric acid, heating to boiling, and
precipitating as bcfore. Filter through the same paper, and wash
thoroughly with the ammonium nitrate solution. Place the paper and
precipitate in a weighed silica, platinum, or Main-Smith crucible, dry,
heat at a low temperature until the carbon has been destroyed, and finally
ignite with a Meker type of burner (at approximately 1000 C.). Allow
to cool in a desiccator over concentrated sulphuric acid or phosphoric
oxide, and weigh rapidly after 25 minutes. Repeat the ignition until
constant weight is attained. Weigh as BeO.
A'. Determination of beryllium by hydrolysis with ammonium nitrite.
Procedure. Neutralise the feebly acid solution, containing about 01 g.
of BeO per 100 mI., cautiously with sodium carbonate, and remove the
resultant slight opalescence with a few drops of dilute acid. Heat the
solution to 70 C., pass a current of air through it, and add, with stirring,
50 ml. of 6 per cent ammonium nitrite solution and 20 ml. of methyl
alcohol for each 01 g. ofBeO expected to be present. Any acid-forming
oxides of nitrogen are thus remov'3d as methyl nitrite. The solution
becomes cloudy. after a few minutes. Complete the precipitation by
boiling gently for 30 minutes. Add a further 10 ml. of methyl alcohol,
and, after 10 minutes, filter through a Whatman No. 41 or 541
filter-paper, wash thoroughly with hot water, dry, and ignite as in A.
Weigh as BeO. /
A". Determination of beryllium by means of tannin. Procedure.
The solution (300-400 mT.) should be weakly acid, free from all cations
other than those of alkali metals, and contain at most 01 g. of BeO.
Add 20-30 g. of ammonium nitrate, heat to boiling, and treat with 10
per cent aqueous tannin solution (use ten times as much tannin as
there is BeO present) with constant stirring, followed by ammonia
solution, dropwise, until precipitation is complete, (the solution should
be just basic to litmus-paper). The precipitate is bulky but not gelatin-
ous, is readily filtered, and shrinks to a relatively small volume on
suction. Filter on a Whatman No. 40 or 540 filter-paper resting
upon a Whatman filter-zone (hardened, No. 51), and apply suction.
Wash with hot water. If alkali metals are present, wash the precipitate
back into the beaker, dissolve in a little hydrochloric or sulphuric acid,
and precipitate the boiling solution with ammonia solution as before.
Filter, dry the paper, and precipitate at 100-130 C., transfer to a
weighed silica, platinum, or Main-Smith crucible, ignite, add a few
drops of concentrated nitric acid (to remove any organic matter which
may be present), ignite strongly, allow to cool in a desiccator, and
rapidly weigh as BeO.
B. Determination of beryllium in the presence of AI, Cr, Fe, Th, and
V by means of tannin. Procedure. The solution should be neutral,
occupy a volume of 300-400 ml. (depending upon the amount of alumin-
452 Quantitative Inorganic Analysis
ium, etc., present, but this should not exceed 01 g.), and contain
30-40 g. of ammonium acetate, and 20-25 g. of ammonium nitrate.
Treat with 15-20 ml. of 2N-acetic acid, boil, and precipitate by the
addition, with stirring, of excess of 10 per cent aqueous tannin solution
or of a 3 per cent solution of tannin in saturated ammonium acetate
solution. Filter the tannin adsorption-complex on a filter-paper with
suction as in A", and wash with dilute ammonium nitrate solution.
Rinse back the precipitate into the beaker by means of a stream of hot
water from a wash bottle, and dissolve it by the addition of dilute
sulphuric acid to the hot liquid. Nearly neutralise the resulting
solution with ammonia solution, and repeat the precipitation as before
with ammonium acetate, ammonium nitrate, and acetic acid. After
the precipitate has settled, decant the clear supernatant liquid through
the filter used for the first filtration, wash the precipitate by decantation
with hot ammonium nitrate solution, transfer it completely to the filter,
and wash with the hot ammonium nitrate solution until the washings
are sulphate-free (test with barium chloride and hydrochloric acid).
Precipitate the beryllium in the filtrate and washings by the addition
of more tannin solution (if necessary), followed by excess of ammonia
solution. Complete the determination as in A". Weigh as BeO.
If ferric iron is present, add a few drops of 10-volume hydrogen peroxide
before precipitating with tannin solution to minimise the chance of any
ferrous iron being formed.
If titanium and/or zirconium are present, precipitation may be effected in
the presence of more concentrated acid because the tannin complexes of these
metals are less soluble; only one precipitation is necessary. The procedure
is as follows. To the cold solution (300 mI.) add ammonia solution until it
produces an incipient cloudiness, then add ammonium acetate (10 g.),
ammonium nitrate (20 g.), and 80 per cent acetic acid (25 mI.). Heat the
solution to boiling, and precipitate the titania and/or zirconia by the addition,
with stirring, of 10 per cent aqueous tannin solution in ten-fold excess of the
weight of the combined oxides. Boil for a few minutes, filter, wash the
precipitate with 10 per cent acetic acid and a little ammonium nitrate.
Determine the beryllium in the filtrate and washings as above.
Note. If anyone of the above metals is present alone with the beryllium
it may be determined by igniting the tannin complex, produced in acetic acid
solution, to the oxide in the usual way.
B'. Determination of beryllium in the presence of aluminium by
means of oxine. Procedure. Precipitate the aluminium from an
ammonium acetate-acetic acid solution (Section lV, 28B), and keep the
filtrate. Heat the filtrate to boiling, and add a very slight excess of
dilute ammonia solution. Filter off the precipitated beryllium hydrox-
ide (preferably after the addition of macerated filter-paper in the form
of a Whatman accelerator or one-third of an ashless tablet), which is
coloured yellow or brown by adsorbed oxine, through a Whatman No.
41 or Ml filter-paper, wash thoroughly with a hot dilute solution
of ammonium acetate containing a few drops of ammonia solution, and
complete the determination as in A.
lV,30. CHROMIUM
Discussion. Chromium may be determined in one of the following forms:
A. Chromic oxide, Cr 20 3 The chromium must be present in solution as a
chromic compound. It can be precipitated as the hydroxide exactly as
Gravimetric Analysis 453
described under Aluminium in Section IV, 9 by means of the smallest possible
excess of ammonia solution (the precipitate is appreciably soluble in excess
of ammonia solution) in the presence of excess of ammonium salts. It is
important to adjust the pH of the solution because of the amphoteric char-
acter of hydrated chromic oxide; the colour of the solution prevents the
use of internal indicators, so that electrometric methods must be used; how-
ever, the indicator (methyl red) may be used" externally."
The KI-K103 method (Section IV, 28) gives a more easily filterable
precipitate:
2CrC13 + 6H 20 ~ 2Cr(OHh + 6HCl
6HCl + 5KI + KI0 3 = 3H 20 +31 2 +
6KCl
The basic benzoate method (Sections IV, 28C and IV, 8) may also be used.
Good results are obtained by precipitation based upon the slow hydrolysis
of potassium cyanate; this yields a granular precipitate of chromic hydroxide
which is readily filtered and washed. This procedure will accordingly be
described in detail.
A disadvantage of the chromic oxide method is that the results obtained
are frequently a few tenths of a per cent too high on account of the formation
of small amounts of chromic chrQIllate, Cr 2 (Cr0 4 h. For highly accurate
results the precipitate should be ignited and allowed to cool in hydrogen.
B. Mercurous chromate, Hg 2Cr0 4, and subsequent weighing as Cr 20 3 The
chromium must be present as chromate, and the solution should be free
. from chloride and large amounts of sulphate. Upon ignition, mercurous
chromate is converted into chromic oxide. Numerous cations interfere,
hence the method has a very limited application.
C. Barium chromate, BaCr0 4 The chromium must be present as
chromate. The method is of limited application because of the general
insolubility of chromates. Chlorides do not interfere, but sulphates
must, of course, be absent. For further properties of barium chromate,
see Section IV, 45B.
To convert a chromic salt into a chromate, treat the chromic solution con-
tained in a porcelain. dish with several ml. of bromine water, followed by
freshly prepared potassium hydroxide solution until alkaline. Warm until
the odour of bromine disappears. _
To convert a chromate into a chromic salt, acidify the solution with hydro-
chloric acid, and either add excess of freshly prepared saturated sulphurous
acid and boil until all the sulphur dioxide has been removed or add concentrated
hydrochloric acid and a little alcohol, and boil until the odour of acetalde-
hyde can no longer be detected and the solution is green. For practice in
this operation, determination A may be carried out with A.R. potassium
dichromate, previously dried at 180-200 C. for 1 hour. 05 Gram of the
salt is accurately weighed out into a 600-ml. beaker, dissolved in about 150
ml. of water, 5 ml. of concentrated hydrochloric acid and 15 ml. of ethyl
alcohol added, and the whole heated uritil the solution is green and no
.longer smells of alcohol or of acetaldehyde. The solution is diluted to 300
mi., and the chromium precipitated as the hydroxide.
IV,31. IRON
Discussion. Iron may be determined in the following forms:
A. Ferric oxide, Fe 20 3 The precipitation of iron as ferric hydroxide by
ammonia solution, etc., and its conversiop into ferric oxide, in which form it
is weighed, is fully described in Section IV, 8. Precipitation with ammonia.
solution yields a gelatinous precipitate which is somewhat difficult to wash
and to filter; this difficulty is partly overcome by the use of macerated
filter-paper.
There are, however, three methods of precipitation which yield ferric
hydroxide in a relatively dense and granular form, which is easily washed
and filtered. These are:
(i) The potassium cyanate method. This has already been discussed under
Chromium, Section IV, 30.
(ii) The hexamethylenetetramine' method. This is based upon the slow
hydrolysis of hexamethylenetetramine in acid solution:
+ 6H 0
2FeC1 3 2 ~ 2Fe(OH)a +6HCl
+ 10H 0
(CH 2 )sN4 2 ~ 6HCHO (formaldehyde) + 4NH 0H4
Separation of ferric iron is effected from manganese, zinc, cobalt, and nickel,
but not from aluminium, chromium, and titanium, which are precipitated.
If calcium is present, there is no risk of co-precipitation as carbonate, as
when ammonia solution is used, for the latter reagent frequently contains
traces of carbonate.
(iii) The hydrazine hydrate method. This procedure is particularly
valuable in the separation of ferric iron from manganese. Precipitation
must be carried out in neutral or slightly alkaline solution, for in acid solution
reduction to the ferrous state occurs.
Full experimental details for each of these methods will be given.
Attention is directed to the fact that if ignition is carried out in a platinum
crucible at a temperature above HOO C. some reduction to triferric tetroxide
Fe 30 4 may occur, and at temperatures above 1200 C. some of the oxide may
be reduced to the metal and alloy with the platinum. This accounts in part
for the contamination of the platinum crucible by iron which sometimes
occurs in analytical work. No magnetic oxide of iron is produced if Main-
Smith crucibles (Section II, 36B) are employed for the ignitions.
B. Ferric cupferron and subsequent weighing as ferric oxide. Cupferron,
the ammonium salt of nitrosophenylhydroxylamine, CsHsN(NO)ONH4'
precipitates iron, vanadium, titanium, and zirconium from strongly acid
solutions, thus affording a separation from aluminium, chromium, beryllium,
phosphorus, boron, manganese, zinc, nickel, cobalt, and sexivalent uranium
(compare Section I, 62B). Copper and thorium must be precipitated from
weakly acid solutions. Several metals (e.g., lead, silver, mercury, bismuth,
tungsten, and cerium) interfere, but most of these may usually be removed
by other methods-for example, by hydrogen sulphide in acid solution.
The precipitate cannot be weighed as such, but must be ignited to the oxide.
456 Quantitative Inorganic Analysis
The ignition must be very carefully carried out in the early stages in order
to avoid mechanical losses, for wet precipitates tend to liquefy and effervesce,
whilst dry precipitates give off considerable volatile matter. The precipitate
is rather bulky, and the amount of material taken should therefore be such
as to yield 01-02 g. of ferric oxide.
C. Ferric 8-hydroxyquinolinate (oxinate). Although subject to interference
by numerous elements, this determination is of interest, as it provides a
method of producing a crystalline ferric complex, which can be collected
upon a filter-crucible and weighed after drying at 135 C. Co-precipitation
of aluminium may be prevented by maintaining the pH at 35-40 by the
use of a buffer solution containing ammonium acetate and tartaric acid.
The experimental details given below refer to a solution of a ferric salt free
from interfering elements.
Treat 25 ml. of the ferric solution (containing about 003 g. of Fe) with
dilute ammonia solution until a faint precipitate persists, and dissolve the
precipitate in the minimum volume of ca. N-hydrochloric acid. Then add
a solution of 3 g. of ammonium acetate in 125 ml. of water, followed by
oxine solution (2 per cent in N-acetic acid) from a burette with constant
stirring until an excess is present: 12-15 ml. are required. Digest the
dark precipitate at 80-90 C. (water-bath) for 30 minutes, filter through a
sintered-glass crucible (porosity No.3), wash successively with 1 per cent
acetic acid and water, and dry to constant weight at 130-140 C. Weigh as
Fe(C 9H 60 N h
A. Determination of iron as hydroxide by hydrolysis of potassium
cyanate. Procedure. The solution (200 ml.) should contain 015-
020 g. of Fe in the ferric state. Add a few drops of concentrated
hydrochloric acid, and heat to boiling (1). Add a concentrated
aqueous solution containing 2 g. of potassium cyanate to the boiling
solution as rapidly as possible, with vigorous stirring (2). Boil the
solution for 2-3 minutes, and allow the precipitate to settle. Wash well
by decantation with hot water, filter off, and complete the determination
as in Section IV, 30A. It is better to ignite the wet filter-paper and
precipitate in a Main-Smith crucible. Weigh as Fe 2 0 3
Notes. 1. If the yellowish solution darkens during heating, add more
hydrochloric acid to bring back the solution to the original colour.
2. The cyanate solution cannot be added all at once, for frothing will then
be excessive. It is important that the ferric hydroxide sol stage be passed
through as quickly as possible.
A'. Determination of iron as hydroxide by means of hexamethYlene-
tetramine. Procedure. The solution (200 mI.) should be faintly acid
and contain about 01 g. of Fe in the ferric state. To the cold solution
add 20 g. of ammonium chloride, followed by excess of a 10 per cent
aqueous solution of hexamethylenetetramine with stirring. Allow
the precipitate to settle, decant the mother liquor through a What man
No. 41 or 541 filter-paper, wash the precipitate by decantation with
hot water, transfer to the filter (1), and again wash with hot water.
Ignite the precipitate and weigh as Fe 20 3
Note. 1. If a tenacious film of the precipitate adheres to the beaker,
dissolve it in a few drops of concentrated hydrochloric acid, and re-precipitate
with ammonia solution.
A". Determination of iron as hydroxide by means of hydrazine
hydrate. Procedure. The solution (100 mI.) should contain about
Gravimetric Analysis 457
01 g. of Fe in ferric state. Add 8 g. of ammonium chloride, a few drops
of methyl-red indicator and neutralise with ammonia solution (methyl
red turns yellow). Then add in one operation a slight excess of hydra-
zine hydrate solution (1), and boil for a short time. Filter through a
Whatman No. 41 or 541 filter-paper, wash with hot water containing
1 g. of ammoniu~chloride and 1 mI. of hydrazine hydrate per 100 mI.,
and then with hot water. Dry and ignite in the usual way. Weigh
as Fe 20 3
Note. 1. Prepared by adding 4 ml. of hydrazine hydrate (poisonous) to
100 ml. of water.
B. Determination of iron with cupferron. Procedure. The solution
(1) (150-200 mI.) should contain about 01 g. of Fe in the ferric state
and be strongly acid with hydrochloric acid or sulphuric acid. To the
cooled solution '(ca. 10 C.) add a freshly prepared, filtered 5 per cent
aqueous cupferron solution (2) slowly and with constant and vigorous
stirring until no further formation of a brown precipitate takes place.
The formation of a white precipitate of nitrosophenylhydroxylamine
indicates when the reagent is present in excess. Do not warm, since
the reagent is rapidly decomposed in hot acid solution. Add a What-
man accelerator (or a third of a Whatman ashless tablet), stir for 2-3
minutes, and without further delay filter through a Whatman No. 41
or 541 filter-paper, preferably supported upon a Whatman filter-
cone. Wash several times with 10 per cent by volume of hydrochloric
acid containing 15 g. of cupferron per litre, then twice with 5N-
ammonia solution to remove excess of cupferron, and finally once with
water. Ignite the precipitate with the paper in a weighed porcelain,
silica, or platinum crubible (best in a Main-Smith crucible, Section
II, 36B) very gently at first until all the organic matter is destroyed,
and then strongly to constant weight. Weigh as Fe 20 3
Notes. 1. A suitable solution for practice may be prepared by weighing
out accurately 08-09 g. of A.R. iron alum, dissolving it in 150 ml. of water,
and adding 25 ml. of concentrated hydrochloric acid.
2. Only freshly prepared solutions should be employed, because the solution
only keeps for a day or two. The dry reagent should be kept in a cool, dark
place, and preferably with a bag of ammonium carbonate suspended in the
bottle.
IV,32. NICKEL
Discussion. oe determined in one of the following forms:
Nickel may
A. Nickel dimethylglyoxime, Ni(C 4H 70 2N2)2' Full details of this estima-
tion are given in Section IV, 12.
B. Nickel salicylaldoxime, Ni(C 7H 60 2N)2' The complex is precipitated
in neutral or very faintly acid solutions (best at pH = 7) in contrast to that
of copper (Section IV, 19C), which is formed in the presence of acetic acid.
The experimental details are similar to those already given for copper,
except that the solution must be neutral or very faintly acid. Experimental
details for the separation of copper and nickel with salicylaldoxime are given
below. Ferric iron interferes, and should therefore be absent.
C. [Ni(C 5H 5N)4](CNS)2; pyridine method. This is a rapid method, similar
in advantages and limitations to those described for copper (Section IV,
19E), cobalt (Section IV, 33D), and zinc (Section IV, 34D). A determination
may be completed in about 30 minutes.
458 Quantitative Inorganic Analysis
D. Nickel dicyandiamidine, Ni(C 2H sON4 )2. When a solution of a nickel
salt is made strongly alkaline with ammonia solution and treated with sodium
or potassium hydroxide solution and dicyandiamidine sulphate, * a yellow or
orange precipitate of the nickel dicyandiamidine complex, Ni(C 2H sON4 )2' is
obtained. This may be weighed after drying at 120-130 C. It is usually
preferable to dissolve the precipitate in excess of standard OIN-hydrochloric
acid and to titrate the excess of standard acid with standard OIN-sodium
hydroxide solution in the presence of methyl red as indicator:
Ni(C 2H 50N4 )2 + 4HCI = 2(C 2H 60N4 ,HCI) + NiCl 2
1 ml. OIN-HCl == 0001467 g. Ni
This provides an excellent method for the volumetric determination of nickel.
Moderate amounts of iron, aluminium, chromium, zinc, cobalt, titanium,
and zirconium do not interfere, but copper (which gives a red precipitate,
Cu(C 2H 50N4)2) must be absent. Cobalt gives a red-violet coloration and, if
present in high concentration, should be converted into the cobaltic state
by oxidation with hydrogen peroxide in ammoniacal solution or its co-
precipitation prevented by the addition of sucrose. The addition of hydraz-
ine sulphate is said to prevent the precipitation of manganese as the hydrated
dioxide.
Nickel may be determined in nickel steel by first rempving the iron as
chloride by ether extraction (Section 1, 73B) or by the basic acetate method
(Section I, 6IB).
E. Metallic nickel. Experimental details of the electrolytic method are
given in Section IV, 81.
B. Determination of nickel in the presence of copper with salicyl-
aldoxime. Procedure. Treat the solution, free from mineral acid and
containing both nickel (not more than 003 g.) and copper (about 003 g.),
with 1 g. of sodium acetate and 10 ml. of glacial acetic acid per 100 ml.
of solution. t Add excess of salicylaldoxime reagent over the quantity
required to precipitate both metals, and stir the solution vigorously
during the addition. Filter off the precipitated copper complex on a
weighed filter-crucible (Gooch, sintered-glass, or porous-porcelain),
wash well with cold water, and dry at 100-105 C. to constant weight.
Weigh as Cu(C7H 6 0 2N)2. Calculate the weight of copper present.
Add dilute ammonia solution to the filtrate and washings (diluted to
350-400 ml.) until the solution is very faintly acid or alkaline. Stir
thoroughly to coagulate the precipitate of nickel salicylaldoxime.
Filter through a weighed, sintered-glass or porous-porcelain crucible,
wash with cold water until the washings give no coloration with ferric
chloride solution, and dry at 100 C. to constant weight. Weigh as
Ni(C 7H 6 0 2N)2. Calculate the weight of nickel present.
C. Determination of nickel by the pyridine method. Procedure. The
solution (100 ml.) should contain about 01 g. of nickel (1) and be neutral
in reaction. Stir in 05-10 g. of A.R. ammonium thiocyanate, heat to
boiling, add 1-2 ml. of pure pyridine, and immediately remove the
flame. Stir for 2-5 seconds until the precipitate commences to separate
in sky-blue prisms. (The precipitate separates immediately or after
standing a short time, according to the quantity of nickel present.)
WhBn cold, filter through a weighed, sintered-glass or porous-porcelain
crucible, and use Solution 1 to assist in the transfer of the precipitate
* Dicyanodiamidine or guanyl urea, H 2 N-C(==NH)-NHCONH 2 == C.H.ON.
t The best pH range for the precipitation of copper in the presence of nickel is 26-31.
'Gravimetric Analysis 459
to the crucible. WashJfour to five times with Solution 2, then twice
with 1-mL portions ,of Solution 3, and finally five or six times with I-mI.
portions of Solution 4. Dry in a vacuum desiccator at room temperature
for 10 minutes and weigh. Repeat the drying until the weight is
constant. Weigh as [Ni(C 5H 5N)4](CNS)2 (2).
Solution 1. 100 Ml. of water containing 04 g. of NH~ONS and 06 ml. of
pyridine.
Solution 2. 615 'Ml. of water, 370 m!. of 95 per cent alcohol, 01 g. of
NH 40NS, and 15 ml. of pyridine.
Solution 3. 10 Ml. of absolute alcohol and 05 ml. of pyridine.
Solution 4. 2J Ml. of absolute (sodium dried) ether and 2 drops of pyridine.
Notes. 1. For practice in this estimation, the student may employ 03 g.,
accurately weighed, of A.R. nickel sulphate or pure nickel ammonium
sulphate.
2. For further experimental details, see under Oopper and Zinc.
D. Determination of nickel with dicyandiamidine sulphate. Pro-
cedure. A. Nickel in a nickels alt. Weigh out accurately about 04 g. of
pure nickel ammonium sulphate, NiSO 4(NH4)2S0 4,6H 20, into a 250-mI.
beaker, dissolve it in a little water, add 6 ml. of concentrated ammonia
solution, followed by 50 m!. of 3-4 per cent aqueous dicyandiamidine
sulphate solution. Cool, and add 20 per cent potassium hydroxide
solution (about 5 m!. are required) with. constant stirring until the
solution acquires an orange colour. The orange (yellow) complex
soon separates. Allow to stand for a few hours, or overnight. Filter
through a sintered-glass crucible (porosity No.3), wash with 2 per cent
ammonia solution, then with a little alcohol, and dry to constant
weight at 120-130 C. Weigh as Ni(C2H50N 4)2' The precipitate is
slightly hygroscopic so that rapid weighing is desirable.
It is preferable to employ tlfe volumetric method. Filter off the
precipitate through a sintered-glass crucible: use the rubber-ring
adapter shown in Fig. II, 31, 3, to support the crucible. Wash the
precipitate with 2 per cent ammonia solution to remove free potassium
hydroxide solution, and then with rectified spirit until free from ammonia
solution (test with mercurous nitrate paper). Remove the crucible
from the rubber adapter, invert it, place it centrally over the rubber
ring and apply suction: upon directing a stream of water from a wash-
bottle on to the sintered-glass disc, the precipitate is completely trans-
ferred to the filter-flask. Introduce 50 m!. of OlN-hydrochloric acid
and a few drops of methyl-red indicator into the flask, swirl the liquid
gently until the precipitate dissolves, and titrate the excess of acid with
O'lN -sodium hydroxide. Calculate the percentage of nickel in the salt.
1 m!. O'IN-HCl == 0001467 g. Ni
B. Nickel in nickel steel (compare Section IV, 12B). Weigh out
accurately about 1 g. of the nickel steel, dissolve it in about 10 m!. of
concentrated hydrochloric acid, and add about 3 mI. of concentrated
nitric acid to oxidise the ferrous iron. Boil the solution to complete
the oxidation and remove nitrous fumes. Dilute to 200 mI., add a
dilute solution of sodium carbonate from a burette, slowly and with
stirring, until a slight opalescence persists. Just dissolve the pre-
cipitate by the addition of glacial acetic acid (ca. 3 mI.), then dilute
4tiU ~uantitative inorganic Analysis
with a further 500 ml. of water, heat to the boiling point, introduce 6 ml.
of 30 per cent sodium acetate solution and boil for 1 minute only. Add
a Whatman " accelerator," allow the precipitate to settle for 3 minutes,
filter, and wash the precipitate three times with 5 per cent sodium
acetate solution. Set the combined filtrate and washings (F) aside.
Puncture the apex of the filter with a glass rod, and wash the precipitate
into the original beaker with warm dilute hydrochloric acid (1 : 1).
Re-precipitate exactly as before by neutralisation of the acid with
sodium carbonate solution, addition of sodium acetate solution, etc.
Combine the filtrate and washings from the re-precipitation with (F),
and evaporate on a hot-plate to a volume of about 100 ml. Add
5 ml. of dilute ammonia solution, 1 g. of dicyandiamidine sulphate, and
1 g. of sodium potassium tartrate, and stir. When the solids have
dissolved, precipitate the nickel dicyandiamidine complex by adding,
with stirring, 20 ml. of 20 per cent potassium hydroxide solution.
Complete the determination as detailed under A.
Calculate the,.percentage of nickel in the sample of nickel steel.
The following alternative procedure may be used to remove most of
the iron in the solution prior to precipitation of the nickel complex.
It is based upon the fact that ferric chloride is soluble in diethyl ether,
whereas the chlorides of a number of other elements (including nickel) .
are insoluble or $0 slightly soluble as to cause little or no concern. First
prepare the following solutions: (a) dilute concentrated hydrochloric
acid with distilled water to a specific gravity of 110 (use a hydrometer);
(b) saturate the diluted hydrochloric acid with alcohol-free ether by
adding small portions of ether with cooling and shaking until a layer
of ether remains on top of the acid (about 30 ml. of ether are required
for 100 ml. of acid).
Weigh out accurately about 1 g. of the nickel steel, dissolve it in
10 ml. of concentrated hydrochloric acid, and oxidise the ferrous iron
by adding 3 ml. of concentrated nitric acid. Evaporate the solution
to a volume of 5 ml., cool, transfer to a 250-ml. separatory funnel with
the aid of 40-50 ml. (in small portions) of solution (a). Cool the
solution to about 5 C., introduce 30 ml. of alcohol-free ether, cool to
5 C., stopper the funnel, and shake gently for several minutes to extrac~
the ferric chloride. Allow to stand for 5 minutes and run off the aqueous
layer into another 250-ml. separatory funnel. Wash the residual ether
layer with three 5-ml. portions of solution (b), and draw off the aqueous
solution obtained after each washing to the second separatory funnel.
Extract the aqueous layer in the latter with 15 ml. of ether, and draw off
the aqueous layer into a 600-ml. beaker: wash the ether layer with three
5-ml. portions of solution (b) and, as before, run off the aqueous phase
(after settling) into the beaker. Evaporate the aqueous solution
almost to dryness on a low-temperature hot-plate (caution i), add 100
ml. of water, 1 g. of sodium potassium tartrate, 1 g. of dicyandiamidine
sulphate, and 5 ml. of concentrated ammonia solution, and warm until
dissolved. Precipitate the nickel dicyandiamidine complex with 20
ml. of 20 per cent potassium hydroxide solution, and allow to stand
overnight. Filter and complete the determination as under A.
Calculate the percentage of nickel in the steel.
Gravimetric A "a lysis 461
IV,33. COBALT
Discussion. Cobalt may be separated in one of the following forms:
A. Cobalt ce-nitroso-~-naphthol complex, weighed as C080 4 or as Co. ce
Nitroso~.naphthol gives a red precipitate with solutions of cobalt salts.
There is some doubt as to the exact composition of the precipitate: the
composition Co(C lO H 6 0 2N)3 has been assigned to it, but it is probably not
pure. The complex is best converted into cobalt sulphate, CoS0 4, or into
metallic cobalt, and weighed in either of these forms. For the limitations of
the method, see Section I, 62F.
An important application is to the separation of nickel and cobalt: a
double precipitation is desirable when nickel is present in large amount.
B. Cobalt anthranilate, Co(C 7H s0 2N)2' In the absence of numerous inter
fering elements (see Section I, 62L) cobalt can be precipitated in neutral or
faintly acid solution by sodium anthranilate as the complex Co(C 7H s0 2N)2'
which is weighed after drying at 105-110 C.
The procedure may be employed to determine the cobalt which remains
after nickel has been precipitated with dimethylglyoxime. The filtrate is
evaporated down with sulphuric acid until fumes of sulphur trioxide appear,
the solution is diluted, the pH adjusted, and the cobalt precipitated as the
anthranilate.
C. Cobalt phenylthiohydantoate complex. Phenylthiohydantoic acid pre
cipitates cobalt in ammoniacal solution in the presence of citrate as a red
brown complex of somewhat indefinite composition. The precipitate
may be ignited to the oxide" C0 30 4 " of uncertain composition, the latter
fused with potassium pyrosu!phate, and the cobalt in the aqueous extract
determined by any of the other methods given in this Section. For the
limitations and advantages of the method, see Section I, 62G.
D. [Co(C 5H 5N)4](CN8)2; pyridine method. If a dilute neutral solution
of a cobalt salt is treated with ammonium thiocyanate and pyridine, tetra
pyridine cobalt dithiocyanate is quantitatively precipitated. The precipitate
is collected and washed, inter alia, with alcohol and ether containing a little
pyridine, and then dried by simply leaving in a vacuum desiccator for 5-15
minutes. A complete determination of cobalt may be carried out in about
30 minutes. The precipitate may be kept unchanged for several hours in a
vacuum desiccator. The method can be applied in the presence of the
alkali metals, magnesium, and the alkaline.earth metals, but copper, cad
mium, nickel, manganese, and zinc must be absent. Large quantities of
ammonium salts must be absent, since these exert a slight solvent action
upon the precipitate. If the solution is strongly acid, it should be evaporated
. to' dryness and the residue dissolved in water.
E. Metallic cobalt. The electrolytic method is discussed in Section IV,
82.
A. Determination of cobalt with a-nitroso-~-naphthol. Procedure.
Dilute the solution containing not more than 01 g. of Co as chloride or
as sulphate (1) to 200 m!., add sufficient concentrated hydrochloric acid
to give a total of 5 m!. of the concentrated acid in the solution, and warm
to about 80 C. Add the freshly prepared IX-nitroso-~-naphthol reagent
(for preparation, see Section I, 62F) until precipitation is considered
complete: about 025 g. of IX-nitroso-~-naphthol are required for each
001 g. of Co. Heat to gentle boiling with stirring until the precipitate
coagulates or settles out. The supernatant liquid should be clear and
yellow. Test whether precipitation is complete by adding a little
more of the reagent to the clear solution. Allow to stand for 2-3 hours
and decant the. clear solution through a quantitative filter-paper (e.g. ,
462 Quantitative Inorganic Analysis
Whatman, No. 541). Wash the precipitate by decantation with a
little warm (ca. 80 C.) dilute hydrochloric acid (1 : 2), finally transfer
the precipitate to the filter-paper, and wash with hot water until free
from acid. Dry the bulky precipitate at 100-110 C. for 1 hour; it will
shrink considerably. Place the dried filter-paper and precipitate in a
silica crucible provided with an interior-fitting serrated lid (Fig. II, 36,
2) just cover the precipitate with A.R. oxalic acid (this will prevent
sudden decomposition of the complex and consequent mechanical loss
during the ignition process) and heat gently until all the organic matter
has burned off. Ignite the precipitate for a few minutes, allow to cool,
treat with a few drops of concentrated nitric acid to oxidise any residual
carbon and to convert the oxide into nitrate: heat carefully until the
excess of nitric acid has been expelled. Finally, add enough sulph~ic
acid to convert the nitrate into sulphate, heat cautiously until the
excess of acid has been expelled, and then for a few moments to very pale
redness (450-500 C.). Allow to cool, moisten with a drop or two of
water, and again heat cautiously as before to expel any free sulphuric
acid. Allow to cool in a desiccator and weigh as cobalt(\us sulphate,
CoS0 4
In an alternative procedure, the tlObalt is weighed as the metal.
Transfer the dried precipitate and filter-paljer to a Rose CJucible (Fig.
IV, 34, 1). Ignite the precipitate and filter-paper in the presence of
oxalic acid as before: it is important to heat very slowly at first and
subsequently to oxidise any residual carbon with a little concentrated
nitric acid. Fit a Rose crucible-cover on to the crucible, and continue
the ignition in a stream of pure hydrogen for at least 30 minutes.
Withdraw the burner beneath the crucible and, afte.r the crucible is
almost at room temperature, momentarily stop the stream of hydrogen
so as to extinguish the flame burning at the cover. Continue the
passage of the stream of hydrogen until the crucible is at room tempera-
ture, and weigh as metallic cobalt. Repeat the treatment with hydro-
gen (heating period of 30 minutes in hydrogen) until constant weight is
attained.
Note. 1. A suitable solution for practice in this determination may be
. prepared from 01 g., accurately weighed, of A.R. cobaltous sulphate (clear,
uneffioresced crystals) or pure cobalt ammonium sulphate.
B. Determination of cobalt as the anthranilate. Procedure. The
solution should contain not more than 0-10 g. of Co in 250 mI., the pH
should be 45 or higher, and be free from high concentrations of sodium
acetate or ammonium salts. Heat to boiling, add with stirring 15--
20 mi. of 3 per cent sodium anthranilate solution, and continue the
boiling for 5 minutes. Allow to stand for 10-15 minutes, filter on a
sintered-glass or porous-porcelain crucible, wash with cold 015 per cent
sodium anthranilate solution, followed by alcohol, and dry at 105-
110 C. to constant weight. Weigh as Co(C7H 6 0 2N)2'
C. Determination of cobalt with phenylthiohydantoic acid. Pro-
cedure. The cobaltous solution (400 mI.) should contain not more
than 0025 g. of Co and about 7 g. of citric acid. Add concentrated
ammonia solution until the solution is neutral and then a further 10 ml.
Add 07-10 g. of phenylthiohydantoic acid, dissolved in 30 ml. of hot
alcohol, with vigorous stirring. Boil and stir the solution for a few
minutes to cause the precipitate to rise to the surface of the liquid.
Gravimetric Analysis 463
Filter the bulky precipitate through a Whatman No. 41 or 541
filter-paper, wash well with a 05 per cent ammonium citrate solution,
and dry at 100-105 C. The material thus obtained is not pure cobal-
tous phenylthiohydantoate, and upon ignition it gives impure C0 3 0 <1;
nevertheless, if it is ignited in a porcelain crucible over a Meker-type
burner, fairly accurate results are obtained by calculating as if it were
C0 20 3 However, it is usually best to fuse the impure oxide with pure
potassium pyrosulphate, dissolve the cooled melt in water, and deter-
mine the cobalt by methods A or B.
D. Determination of cobalt by the pyridine method. Procedure. The
solution (75-100 mI.) should be neutral and contain about 01 g. of
Co (1). Add 05-10 g. of A.R. ammonium thiocyanate, heat to boiling,
treat with 1-2 mI. of pure pyridine, and remove the source of heat
jmmediately. Stir for 5 seconds, and allow to cool to room temperature.
The solution remains clear for a short time; as the solution cools, red,
shiny crystals of the complex separate. (If the precipitate on the sides
of the beaker exhibits the blue colour of the di-pyridine complex, this
is washed with a little water into the solution when the blue colour
immediately disappears. If stirring is continued for several minutes
after the addition of the pyridine, the compound soon separates in the
crystalline form.) Filter through a weighed, sintered-glass or porous-
porcelain crucible; use Solution 1 to assist in the transfer of the pre-
cipitate to the crucible. Wash the precipitate five or six times with
Solution 2, then twice with I-mI. portions of Solution 3, and finally
eight to ten times with small volumes (1-2 mI.) of Solution 4 (for further
experimental details, see Sections IV, 19E, aoo IV, 34D). Dry in a
vacuum desiccator at room temperature for 10 minutes, and weigh.
Repeat the drying, etc., until the weight is constant. Weigh as
[Co(C 5H 5N )<1] (eNS h
Solution 1.
.
100 Ml. of water containing 05 g. of NH 4CNS and 07 ml. of
pyridine.
Solution 2. 855 Ml. of water, 130 ml. of 95 per cent alcohol, 01 g. of
NH 40NS and 15 ml. of pyridine.
Solution 3. 25 Ml. of absolute alcohol and 2 ml. of pyridine.
Solution 4. 30 Ml. of absolute (sodium dried) ether and 4 drops of pyridine.
Note. 1. For practice in this estimation, the student may employ 03 g.,
accurately weighed, of A.R. cobalt ammonium sulphate or of A.R. cobaltous
sulphate.
If the solution is weakly acid, add ammonium thiocyanate, then pyridine
until a precipitate appears, warm until the precipitate dissolves, add 1-15
ml. of pyridine, and immediately remove the source of heat.
IV,36. VANADIUM
Discussion. This element, as vanadate, may be determined in one of the
following forms:
A. Mercurous vanadate, Hg 3V0 4, and subsequent weighing as vanadium
pentoxide, V20 5 This method is applicable only in the absence of substances
which give precipitates with mercurous nitrate solution (e.g., chromate,
arsenate, molybdate, tungstate, and phosphate). Actually the precipitate
obtained in the determina,tion consists of a mixture of mercurous ortho-
and pyro-vanadates; this is ignited to, and weighed as, vanadium pentoxide.
The solution may contain free nitric acid but not ammonium salts.
B. Silver vanadate, Ag 3V0 4 Vanadates are precipitated by excess of
silver nitrate solution in the presence of sodium acetate, followed by boiling,
as silver orthovanadate. The following reactions occur with a solution of a
metavanadate:
2NaV0 3 + 2Na'C H 0 + H 0 ~ Na V 0 + 2H'C H 30
2 3 2 2 4 2 7 2 2
Na V 0 + 4AgN0 3 ~ Ag V 0 + 4NaN0 3
4 2 7 4 2 7
Volumetric methods (see Chapter III) are, however, more convenient, less
influenced by interfering elements, and are generally preferred.
1V,41. ZIRCONIUM
Discussion. Zirconium may be determined in one of the following forms:
A. Secondary zirconium phosphate, ZrH 2 (P0 4 )2' and subsequent ignition tO'the
pyrophosphate, ZrP 20 7 Zirconium is quantitatively precipitated from
solutions containing 10 per cent by volume of sulphuric acid by a 50-100-fold
excess of diammonium hydrogen phosphate. The precipitate is washed
with a moderate amount of 5 per cent ammonium nitrate solution to remove
excess of phosphate; prolonged washing results in hydrolysis of the zir-
conium phosphate and consequent loss of phosphate, thus introducing errors
which may be as high as 1 or 2 per cent. If titanium is present, excess of
476 Quantitative Inorganic Analysis
hydrogen peroxide must be added before the addition of the phosphate
precipitant. Cerium should preferably be in the tervalent condition; a
double precipitation is required in the presence of thorium. Iron must be in
the ferrous state; uranium and tin interfere and must be absent.
B. Basic zirconium selenite and subsequent ignition to the dioxide, Zr0 2
The zirconium is precipitated as the basic selenite with selenious acid in hot
dilute hydrochloric acid solution, the precipitate washed with dilute hydro-
chloric acid, and then ignited to, and weighed as, Zr0 2 No other acids should
be present, and the hydrochloric acid content should preferably be 5 per cent
and not over 7 per cent by volume. This method enables a separation to be
effected by a single precipitation from the rare earths (cerium being in the
tervalent condition) and from aluminium. Iron, if present up to 10 per
cent of the weight of the zirconium, does not interfere if precipitation is made
in dilute solution (100-200 ml. of solution containing 005 g. Zr0 2 ) and double
the quantity of selenious acid solution is used for precipitation.
In an alternative method the zirconium is converted into the normal
selenite, Zr(Se0 3)2' after digestion at 80-100 C. (Section 01,152) and weighed
as such after drying at 110-150 C.
C. Zirconium n-propylarsonate and subsequent ignition to the dioxide, Zr0 2
Zirconium is quantitatively precipitated in dilute sulphuric acid solution by
aqueous n-propylarsonic acid; tin interferes, but may be removed from the
zirconium oxide residue obtained upon ignition by adding powdered am-
monium iodide, and re-igniting (see Section IV, 22A). Titanium, aluminiuin,
chromium, cobalt, nickel, copper, uranium, vanadium, thorium, molybdenum,
and tungsten do not interfere. Complete precipitation of the zirconium takes
place in the presence of large quantities of iron, but a small quantity of iron
is adsorbed upon the zirconium precipitate; the iron is completely removed
by re-precipitation. The method is therefore of particular value for the
analysis of complex steels containing zirconium. Full particulars are given
in Section IV, 96L; the method for the determination of zirconium in a
simple compound or mixture should be obvious from these details.
D. Zirconium para-hydroxy-phenylarsonate and subsequent ignition to the. di-
oxide, Zr0 2 The procedure is similar to that already given for titanium
(Section IV, 40D); the hydrochloric acid concentration should not exceed
3N and the sulphuric acid concentration 15N. The method permits the
separation in a single precipitation from copper, cadmium, vanadium (V),
molybdenum (VI), uranium (VI), iron (III), aluminium, chromium, nickel,
cobalt, zinc, manganese, bismuth, and the alkaline earths. If ferric iron
is present, ammonium thiocyanate (about 25 g. for a maximum of 100 mg.
of Zr) is added to prevent interference by this element. Phosphates must,
of course, be absent; titanium, thorium, cerium, and tin interfere. The
determination is concluded by heating in hydrogen in a Rose crucible,
followed by ignition in air to the dioxide: the precipitate obtained by
direct ignition may contain arsenic, which is otherwise difficult to remove.
E. Zirconium mandelate and subsequent ignition to the dioxide, Zr0 2
Zirconium may be precipitated from a hydrochloric acid solution with man-
delic acid (C 6 H 5CH(OH)COOH) as zirconium mandelate, Zr(C 8H 70 3 )4'
which is ignited to and weighed as the dioxide. Quantitative separation is
thus made from titanium, iron, vanadium, aluminium, chromium, thorium,
cerium, tin, barium, calcium, copper, bismuth, antimony, and cadmium.
If sulphuric acid is employed, the concentration should not exceed 5 per
cent: higher concentrations give low results.
A. Determination of zirconium as pyrophosphate. Proced7lre. The
zirconium solution should contain about 10 per cent by volume of
sulphuric acid (ca. 3'7N) and not more than 01 g. of Zr. Add a few
ml. of " lOO-volume" hydrogen peroxide to oxidise any titanium
Gravimetric Analysis 477
present and keep it in solution; if titanium is known to be absent, the
addition of hydrogen peroxide is unnecessary. Add a freshly prepared
10 per cent aqueous diammonium hydrogen phosphate s,olution in
50-l00-fold excess: use 10 mI. for every 10 mg. of Zr present, but not
less than 20 mI. Dilute to 300 mI. and adjust the acidity so that it is
about 37N in sulphuric acid (or in hydrochloric acid). Boil the solu-
tion for a few minutes, allow to digest for 15-30 minutes on a water-
bath, and allow to cool to about 60 C. Add a Whatman " accelera-
tor" (or an equivalent quantity of macerated filter-paper) and filter
through a quantitative filter-paper. [If small amounts of Zr 10
mg.) are being determined, allow to stand overnight.] Wash first with
100-150 mI. of 2N-sulphuric acid containing 25 g. of diammonium
hydrogen phosphate in 150 mI., and finally with cold 5 per cent am-
monium nitrate solution until the filtrate is sulphate-free. [If the
solution contains only zirconium and alkali metals, washing with the
ammonium nitrate solution alone suffices.] Dry the filter and pre-
cipitate at 100-110 C., place in a platinum crucible (previously ignited
at 1150 C.) and burn off the filter-paper at as low a temperature as
possible. After most of the carbon has been burnt off, raise the tem-
perature gradually to a dull red heat and finally to 1100-1150 C., for
1-3 hours, preferably in an electric muffle furnace. Weigh as ZrP207'
B. Determination of zirconium with selenious acid. Procedure. The
solution (200 mI.) should contain about 5 per cent by volume of hydro-
chloric acid (sulphuric acid is undesirable) and not more than 02 g.
of zirconia. Treat with 20 mI. of ~25 per cent aqueous selenious acid
solution, and boil for a few minutes. Allow the precipitate of basic
selenite to settle, filter through a quantitative filter-paper, wash with
hot 3 per cent hydrochloric acid containing a little selenious acid, dry
in a weighed porcelain, platinum, or Main-Smith crucible, and ignite
to constant weight. Weigh as Zr0 2
Alternatively, precipitate the zirconium as the normal selenite
(Section III, 152), filter through a sintered-glass crucible (porosity
No.4), wash with hot dilute hydrochloric acid, followed by cold water
until the washings are free from selenious acid, and dry at 110-150 C.
to constant weight. The precipitate contains 2643 per cent Zr.
Some reduction may occur with large quantities of precipitate, leading
to slightly high results. For this reason the volumetric method (Section
III, 152) is preferable.
E. Determination of zirconium with mandelic acid. Procedure. The
solution (20-30 mI.) may contain 0,05-02 g. of Zr, and should possess a
hydrochloric acid content of about 20 per cent by volume. Add 50 mI.
of 16 per cent aqueous mandelic acid solution and dilute to 100 mI.
Raise the temperature slowly to 85 C. and maintain this temperature
for 20 minutes. Filter off the resulting precipitate through a quantita-
tive filter-paper, wash it with a hot solution containing 2 per cent of
hydrochloric acid and 5 per cent of mandelic acid. Ignite the filter
and precipitate to the oxide in the usual manner. Weigh as Zr0 2
IV,42. THALLIUM
Discussion. Thallium may be determined in either of the following forms:
A. Thallous chromate, T1 2Cr0 4 The thallium must be present in the
thallous state. If present as a thallic salt, reduction must be effected with
sulphur dioxide before precipitation; the excess of sulphur dioxide is boiled off.
478 Quantitative Inorganic Analysis
B. Thallous cobaltinitrite, Tl3[Co(N0 2)6]' It, is possible to precipitate a
thallous salt quantitatively by means of a special sodium cobaltinitrite
reagent at 30-40 C. in the presence of 5 per cent of formic acid.
A. Determination of thallium as chromate. Procedure. The solution
(100 mI.) should contain about 01 g. of Tl, no excessive amounts of
ammonium salts, and no substances that form precipitates with
ammonia solution, or reduce potassium chromate, or react with potas-
sium or thallous chromate in ammoniacal solution. Neutralise the
thallium solution (100 mI.) with dilute ammonia solution (2: 1), and add
3 mI. in excess. Heat to about 80 0 C., and add 2 g. of potassium
chromate in the form of a 10 per cent solution slowly and with constant
stirring. Allow to stand at the laboratory temperature for at least 12
hours. Filter through a weighed filter-crucible (Gooch, sintered-glass, or
porous-porcelain), wash with I per cent potassium chromate solution,
then with 50 per cent alcohol, and dry at 120 0 C. to constant weight.
Weigh as Tl 2Cr0 4
B. Determination of thallium as cobaltinitrite. Procedure. The
solution (100 mI.) should contain about 5 per cent of free formic acid,
and about 01-02 g. of Tl; potassium and other elements which give
precipitates with the sodium cobaltinitrite reagent should be absent.
Warm the solution to 30-40 C. and add an excess of the reagent (1) at
the same temperature. Allow to stand for I hour, collect the scarlet
precipitate on a weighed sintered-glass or porous-porcelain crucible,
wash with cold water, and dry at 100 C. to constant weight. Weigh
as TI 3[Co(N0 2)6]' -.
Note. 1. The reagent is prepared by mixing equal volumes of (a) 286 g.
of cobalt nitrite and 50 ml. of 50 per cent formic acid in 500 ml. of water, and
(b) 180 g. of sodium nitrite per 500 ml. of water.
IV,44. STRONTIUM
Discussion. Strontium may be estimated in one of the following forms:
A. Strontium sulphate, SrS0 4 In this determination (the most accurate
for strontium) calcium, barium, and lead must be absent, and the solution
(preferably of the chloride) should be as neutral as possible. If considerable
acid is present, this must be removed by evaporation. Strontium sulphate
dissolves appreciably in an acid,medium because of the reaction:
SrS0 4 + H+ ~ HS0 4 - + Sr++
Strontium sulphate has a solubility of about 014 g. per litre at the ordinary
temperature; the solubility is decreased by the a;ddition of a slight excess of
sulphuric acid, and of alcohol (50 per cent).
B. Strontium oxide, SrO. The strontium is precipitated as the oxalate,
SrC 2 0 4,H 2 0, and is ignited to, and weighed as, the oxide, SrO. The experi-
mental details are similar to those given in Section IV, 10, except that some
alcohol, should be added to reduce the solubility. Calcium, barium,
magnesium, and other interfering elements must be absent.
A. Determination of strontium as sulphate. Procedure. The solu-
tion (100 ml.) should contain about 02 g. of Sr and be very slightly
acid with hydrochloric acid (1). Add slowly a ten-fold excess of dilute
sulphuric acid, followed by a volume of alcohol equal to that of the
solution. Stir well, and allow to stand for art least 12 hours. Transfer
the precipitate to a weighed Vitreosil or porous-porcelain filter-crucible,
wash with 75 per cent alcohol to which a few drops of sulphuric acid
have been added, and finally with pure alcohol (or rectified spirit) until
the washings are free from sulphate. Dry and ignite (crucible-ignition
dish or in a large nickel crucible) at dull redness to constant weight.
Alternatively, a filter-paper may be used: here the paper should be
burnt apart from the precipitate (Section II, 38C) (to prevent possible
reduction of the latter to the sulphide), and the residue then ignited
together with the main precipitate in a weighed porcelain, silica, or
platinum crucible. Weigh as SrS0 4
Note. 1. A solution for practice in this determination may be prepared by
dissolving 03-04 g., accurately weighed, of pure strontium carbonate (the
A.R. product may be obtained from the Mallinckrodt Chemical Works,
U.S.A.) in a little dilute hydrochloric acid (see Section IV, 10), and diluting
to 100 ml.
IV,45. BARIUM
Discussion. Barium may be determined in one of the following forms:
A. Barium sulphate, BaS04. This method is most widely employed.
The effect of various interfering elements and radicals (e.g., cl1lcium, stron-
tium, lead, nitrate, etc., which contaminate the precipitate) has been fully
dealt with in Section IV, 6.
B. Barium chromate, BaCr0 4 This method is of limited application
because of the influence of numerous interfering elements. It is useful,
480 Quantitative Inorganic Analysis
however, in the separation of barium from both calcium and strontium.
Barium chromate may be heated to a red heat without decomposition. If
green spots of chromic oxide, due to the reduction of the chromate, should
appear, continued ignition with free access of air will result in re-conversion
into chromate.
Precipitation of barium chromate is usually carried out in a dilute acetic
acid solution which is buffered with ammonium acetate; a double precipita-
tion is desirable in the presence of much strontium and/or calcium.
A. Determination of barium as sulphate. Procedure. The solution
(100 mI.) should contain not more than 015 g. of barium (1), and
not more than 1 per cent by volume of concentrated hydrochloric
acid. Heat to boiling, add a slight excess of hot N-sulphuric acid slowly
and with constant stirring. Digest on the steam-bath until the pre-
cipitate has settled, filter, wash with hot water containing a few drops
of sulphuric acid, and then with a little water until the acid is removed.
Full experimental details of the filtration, washing, and ignition pro-
cesses are given in Section IV, 6. Weigh as BaS0 4
Note. 1. A suitable solution for practice may be prepared by dissolving
about 03 g., accurately weighed, of A.R. barium chloride in 100 m!. of water
and adding 1 ml. of concentrated hydrochloric acid.
B. Determination of barium as chromate. Procedure 1. The solution
(200 mI.) (1) should contain not more than 04 g. of Ba, and be neutral
in reaction. Add 10 ml. of 6N-acetic acid and 10 ml. of neutral 3N-
ammonium acetate solution to the solution, heat to boiling, and treat
with a slight excess of a hot dilute solution of ammonium chromate
(2) which is added dropwise from a burette with constant stirring.
Place the beaker on a water-bath until the precipitate settles; test for
completeness of precipitation by adding a little more of the reagent.
Allow to cool, filter through a weighed porous-porcelain crucible, wash
with hot water until 1 ml. of the washings gives scarcely any reddJ..sh-
brown coloration with neutral silver nitrate solution. Place ~e
crucible upon a crucible-ignition dish inside a larger porcelain or
nickel crucible, and heat to a temperature not exceeding dull-red
heat until the precipitate has a uniform bright-yellow colour, and is
constant in weight. Weigh as BaCr0 4 .
L
484 Quantitative Inorganic Analysis
saturated with sodium magnesium uranyl acetate and kept at a
temperature of 20 1C. Dry for 30 minutes at 105 C., and weigh
as NaMg(U02)s(C2H302)9,65H20.
Notes. 1. A suitable solution for practice in the determination may contain
23 mg. of Na in 5 ml.
2. The reagent is prepared as follows:
Solution A: 213 g. of crystallised uranyl acetate, 15 g. of glacial acet.
acid, and 230 ml. of water.
Solution B: 125 g. of crystallised magnesium acetate Mg(C 2H 3 0 2)2,6H 20,
15 g. of glacial acetic acid, and 250 ml. of water.
Heat solutions A and B separately to 70 C. until all the salts are dissolved,
and then mix the solutions at 70 C., and allow to cool to 20 C. Place the
vessel containing the mixed reagent in water at 20 1 C., and maintain
at this temperature for 1-2 hours until the slight excess of salts has crystal-
lised out. Filter through a dry filter into a dry bottle. The solution is
stable for prolonged periods (8 months) if kept away from direct sunlight.
Titration may also be carried out with standard ceric sulphate solution.
E. Potassium periodate, KI0 4 Potassium may be quantitatively pre-
cipitated as the periodate by adding periodic acid to a concentrated solution
of the nitrate and then adding a large volume of a mixture of equal volumes
of anhydrous aldehyde-free ethyl alcohol and anhydrous ethyl acetate; the
solution must be maintained at 0 C. and stirred mechanically for 30 minutes.
The precipitated potassium pGriodate may be weighed after drying for
486 Quantitative Inorganic Analysis
10 minutes at 105 C., or it may be dissolved in a boric acid-borax buffer
solution, potassium iodide added, and the liberated iodine titrated with
standard sodium arsenite solution:
IV,49. LITHIUM
Discussion. Lithium, if present as a salt of a volatile acid, may be deter.
mined as lithium sulphate, Li 2S0 4 , by repeated evaporation with sulphuric
acid (see Section IV, 47A). No other elements may be present. Here the
change from the acid sulphate to the normal sulphate takes place CoUl.
pa'ratively easily, so that the addition of ammonium carbonate is not essential.
When present with sodium and potassium as chlorides, the lithium may
be determined:
(a) By the n.butyl alcohol-ethyl acetate method (Section IV, 48B).
(b) By extraction of the lithium chloride with dry isoamyl alcohol or
dioxan (diethylene dioxide) or anhydrous acetone, sodium and potassium
chlorides being sparingly soluble in these solvents. The best results
are obtained with 2-ethylhexanol, although those with n-hexyl alcohol
are usually quite satisfactory. The solubilities of the chlorides in
anhydrous isoamyl, n-hexyl alcohols, and in 2-ethylhexanol (iso-octyl
alcohol), expressed in grams dissolved by 100 mi. of the anhydrous
solvent at 25 C., are-
I
IV,56. CYANIDE
Discussion. This anion is determined as silver cyanide, AgCN; the experi-
mental details are similar to those given for Chloride, except that, owing to
the volatility of hydrocyanic acid, the solution must not be heated. The
cold solution of alkali cyanide is treated with an excess of silver nitrate
solution, faintly acidified with nitric acid, the precipitate allowed to settle,
collected On a weighed filter-crucible, and weighed as AgCN after drying at
110 C.
IV,60. IODATE
Discussion. Iodates are readily reduced by sulphurous acid to iodides;
the latter are determined by precipitation with silver nitrate solution as
silver iodide, AgI. Iodates cannot be converted quantitatively into iodides
~( by ignition, for the decomposition takes place at a temperature at which
l'?;' the iodide is appreciably volatile.
Periodates are also reduced by sulphurous acid, and may therefore be
similarly determined. Similar remarks apply to bromates; these are ulti-
mately weighed as silver bromide, AgBr.
Determination of iodate as silver iodide. Procedure. Acidify the
iodate solution (100 ml. containing ca. 03 g. of 103) (1) with sulphuric
acid, and pass in sulphur dioxide (or add a freshly prepared saturated
solution of sulphurous acid) until the solution which at first becomes
yellow, on account of the separation of iodine, is again colourless.
Boil off the excess of sulphur dioxide, and precipitate the iodide with
dilute silver nitrate solution as described in Section IV, 54. Weigh as
AgI.
Note. 1. For practice in this determination, the student may employ
A.R. potassium iodate.
IV,61. SULPHATE
Discussion. Full details for the determination of soluble sulphates as
barium sulphate, BaS0 4 are given in Section IV, 6. For sulphates which are
insoluble in water and acids, it is best to mix the finely powdered solid with
six to twelve times its bulk of anhydrous sodium carbonate in a platinum
crucible set in an asbestos shield (Section II, 38), heat the covered crucible
slowly to fusion, and maintain in the fused state for 15 minutcs. The melt
498 Quantitative Inorganic Analysis
is extracted with water, the solution filtered, the residue washed with hot 1
per cent sodium carbonate solution, and the cold filtrate carefully acidified
with hydrochloric acid (to methyl orange). The sulphate is determined as
in Section IV, 6. If silica is present, the acid filtrate is evaporated to dryness
on the water-bath to dehydrate the silica; a little concentrated hydrochloric
acid is added, followed by hot water. The silica is filtered off, and the sulphate
determined in the filtrate.
IV,62. SULPHIDE
Discussion. The determination of sulphur in insoluble sulphides by wet
and dry processes and subsequent weighing as barium SUlphate, BaS04 , is
fully dealt with in Section IV, 7. Other methods, which are particularly
applicable to soluble sulphides, include oxidation in alkaline solution with
sodium hypochlorite or hydrogen peroxide,* followed by the estimation of
sulphate as barium sulphate.
IV,63. SULPHITE
Discussion. Sulphites may be readily converted into sulphates by boiling
with excess of bromine water, sodium hypochlorite, sodium hypobromite, or
ammoniacal hydrogen peroxide (equal volumes of 20-volume hydrogen
peroxide and 1 : 1 ammonia solution). The excess of the reagent is decom-
posed by boiling, the solution acidified with hydrochloric acid, precipitated
with barium chloride solution, and the barium sulphate collected and weighed
in the usual manner (Section IV, 6).
IV,64. THIOSULPHATE
Discussion. Thiosulphates are oxidised to sulphates by methods similar
to those described for sulphites (Section IV, 63), e.g., by heating on a water-
bath with an ammoniacal solution of hydrogen peroxide, followed by boiling
to expel the excess of the reagent. The sulphate is then determined as
barium sulphate, BaS0 4 One molecule of thiosulphate corresponds to two
molecules of barium sulphate.
* Ammoniacal hydrogen peroxide is usually employed. The hydrogen peroxide must
be free from sulphate.
Gravimetric Analysis 499
IV,65. ., PHOSPHATE
Discussion. Orthophosphates may be precipitated as magnesium ammonium
phosphate, MgNH 4P0 4,6H 20, by magnesium chloride and ammonium
~hloride in ammoniacal solution (fl""'magnesia" reagent). Most elements,
other than those of the alkalis, interfere, however, by giving precipitates
with" magnesia mixture." It is therefore necessary in the majority of cases
~o separate the phosphate first from interfering substances. This may be
readily effected by precipitation as ammonium phosphomolybdate with excess
of ammoniu)'ll molybdate in warm nitric acid solution: arsenic, vanadium,
~itanium, zirconium, silica, and excessive amounts of ammonium salts inter-
fere. When first precipitated, the yellow precipitate is generally supposed
to contain water and nitric acid of crystallisation; upon drying at 120-160 C.,
~he water and nitric acid of crystallisation are driven off and the precipitate
has the composition (NH4)a[PMo12040] (2). The precipitate thus obtained
is dissolved in dilute ammonia solution, and the phosphate is then precipitated
a,s magnesium ammonium phosphate. A double precipitation of the latter
is necessary in order to obtain a precipitate entirely free from molybdate.
If interfering elements are absent, the original yellow precipitate may be
weighed either as ammonium phosphomolybdate, (NH4)a[PMo12040]' after
drying at 120-160 C. or as phosphomolybdic anhydride, P 20s,24Mo0 3 , after
heating at 400--450 C. for 30 minutes. For practice in this estimation, the
student may determine the percentage of phosphate in anhydrous A.R.
dis odium hydrogen phosphate, Na 2HP0 4, or in any other phosphate supplied
by the instructor. (Most of the experimental details are given in Section
III, 146.) The precipitate of ammonium phosphomolybdate should,
however, be filtered through a weighed porous-porcelain filter-crucible, and
washed with the special wash liquid (1) until only a faint brown colour is
given when 5 ml. of the washings are tested with potassium ferro cyanide
solution. The precipitate is dried at 120-160 C. to constant weight (1-2
hours) and weighed as (NH4)a[PMo12040]. The precipitate may now be
heated in an electric oven at 400--450 C. (or at a dull red heat upon a crucible-
ignition dish) and weighed as P 20s,24Mo0 3 Both solids are appreciably
hygroscopic and should be weighed rapidly.
Notes. 1. Prepared by dissolving 10 g. of ammonium nitrate in water,
adding 8 ml. of concentrated nitric acid, and diluting to 200 ml.
2. The proportion of P found, depending upon the method and the
conditions of precipitation, is 163-164 per cent; the theoretical value is
165 per cent. A factor of 164 per cent is often used.
A. Determination of phosphate as magnesium ammonium phosphate
hexahydrate or as magnesium pyrophosphate. Procedure. To a
neutral or weakly acid solution (50-100 ml.) of the phosphate, contain-
ing not more than 01 g. ofP 20 5 and free from interfering elements (1),
add 3 ml. of concentrated hydrochloric acid and a few drops of methyl-
red indicator. Introduce 25 ml. of magnesia mixture (Section IV,
20B, Note 2), followed by pure concentrated ammonia solution slowly
whilst stirring the solution vigorously until the indicator turns yellow.
The procedure from this stage is the same as described for the deter-
mination of magnesium in Section IV, 11, except that when carrying
out the re-precipitation from the hydrochloric acid solution 2 m!. of
the magnesia mixture are added instead of the 1 m!. of ammonium
phosphate solution. Weigh as MgNH 4P0 4 ,6H 2 0 or as Mg 2P 20 7
Note. 1. A suitable solution for practice may be prepared by dissolving
about 04 g., accurately weighed, of A.R. anhydrous Na 2HP0 4 in 100 ml. of
water.
500 Quantitative Inorganic Analysis
B. Determination of phosphate as magnesium ammonium phosphato
hexahydrate or as magnesium pyrophosphate after a preliminary separa.
tion as ammonium phospho molybdate. Procedure. For practice in
this estimation, it is recommended that basic slag (1) be employed.
Weigh out accurately about 25 g. of the finely powdered basic slag into
a 10-cm. porcelain or Pyrex basin. Add 20 ml. of concentrated sulphuric
acid, and mix to a smooth paste. Heat the mixture on a sand-bath
(or hot-plate) in the fume cupboard until white fumes begin to appear,
and then keep it in this condition for 45 minutes with stirring at inter-
vals. Avoid strong fuming of the sulphuric acid. Allow to cool,
dilute carefully with water, and, when cold, filter into a 250-ml. volu-
metric flask, wash the residue thoroughly with cold water, and make
up to the mark. Measure out 50 ml. of the solution (do not allow the
solution to stand too long, as calcium sulphate is liable to crystallise
out) into a 400-ml. beaker, add 10 ml. of concentrated nitric acid,
followed by 1 : 1 ammonia solution until a faint permanent precipitate
appears. Re-dissolve the precipitate by the addition of a few drops
of concentrated nitric acid, heat to 40-45 C. (use thermometer), and
treat with 100 ml. of the ammonium molybdate reagent (Section III,
146) previously heated to the same temperature, slowly and with
stirring; continue the stirring for ahout 10 minutes. Al10w the pre-
cipitate to stand for a few hours, but preferably overnight. Filter
through a Whatman No. 40 or 540 filter-paper, leaving as much
as possible of the precipitate in the beaker, and wash the precipitate
moderately with 5 per cent ammonium nitrate solution. Pour down
the sides of the beaker containing the main part of the ammonium
ph03phomolybdate precipitate a solution prepared by dissolving 05 g.
of citric acid in 15 ml. of water and 7 ml. of concentrated ammonia
solution. (The citric acid serves to keep any iron in solution.) When
the precipitate has dissolved, pour this solution slowly into the filter-
paper containing the reml_Linder of the precipitate; collect the filtrate
and washings in a 400-ml. beaker. Wash the original beaker and filter-
paper successively twice each with small volumes of dilute ammonia
solution(1 : 20), hot water, hot dilute hydrochloric acid (1: 20), hot
water, and finally with dilute ammonia solution (I : 20) and hot water.
The filtrate and washings should not exceed 200 ml. in volume at this
stage. (The above treatment is necessary for the complete removal of
the last traees of phosphate from the paper.) Render the ammoniacal
solution slightly acid (methyl red) with dilute hydrochloric acid, and
introduce 25 ml. of magnesia mixture (Section IV, 20B, Note 2) dropwise
and stirring continuously. Next add 10-15 ml. of 1: 1 ammonia
solution slowly and with stirring. Allow the solution to stand for at
least 4 hours, but preferably overnight. Filter without attempting to
transfer the precipitate, wash the vessel, residue, and paper a few times
with 1 : 20 ammonia solution. Dissolve the precipitate on the filter in
25 ml. of warm I : 4 hydrochloric acid, and collect the solution in the
original beaker containing the bulk of the precipitate. Wash the filter-
paper thoroughly with warm I : 20 hydrochloric acid. Add to the filtrate
and washings, diluted to 100 ml., 2 ml. of magnesia mixture; then re-
precipitate the phosphate by the addition of 1 : I ammonia solution
drop by drop and with thorough stirring, and finally add 10 ml. of the
1 : I ammonia solution in excess. Allow to stand for 12 hours. Collect
the precipitate on a filter-paper or in a weighed silica, Gooch, or porous-
Gravimetric Analysis 501
porcelain crucible, and wash with cold 1 : 20 ammonia solution until
free from chloride. Complete the determination as described in
Section IV, 11, and weigh as MgNH 4P0 4 ,6H 2 0 or as Mg 2P 2 0 7
Note. 1. Ridsdale's "Basic Slag (Thomas Phosphate), No. 31 " (one of
the Analysed Samples for Students) or the Bureau of Analysed Samples
" Basic Slag No. 174A " (one of the British Chemical Standards) is suitable.
IV,67. HYPOPHOSPHITE
Discussion. This anion is determined similarly to phosphite either
as mercurous chloride, Hg 2Cl z, or as ammonium phosphate hexahydrate,
MgNH 4P0 4,6H zO, or as magnesium pyrophosphate, Mg ZP 20 7 In this case the
reaction with mercuric chloride solution is :
4HgCI:i + H aP0 + 2H 0
2 2 = 2Hg zCl 2 + H aP0 + 4HCI
4
so that 2Hg 2Cl 2 "" H 3PO Z
IV,69. BORATE
Discussion. The most trustworthy methods for the determination of
borate are based upon its volatilisation as methyl borate, B(OCHala; this is
achieved by acidifying the alkali or alkalineearth borates and heating with
absolute methyl alcohol (methanol). The methyl borate is saponified by
bringing it in contact with a weighed amount of lime in the presence of water:
B(OCH3h + 3HOH = (BOH)3 + 3CH30H
The boric acid is set free and combines with the lime to form calcium borate.
If the paste is then evaporated to dryness and ignited, the increase in weight
represents the amount of B 20 3. Alternatively, the boric acid is titrated
after the addition of mannitol as described in Section III, 17. For complete
details, the reader is referred to other treatises (1).
Note. 1. For example: W. F. Hillebrand and G. E. F. Lundell, Applied
Inorganic Analysis, 1929, p. 611; J. W. Mellor and H. W. Thompson, A
Treatise on Quantitative Inorganic Analysis, 1938, p. 659; W. D. Treadwell,
Tabellen und Vorschriften zur Quantitativen Analyse, 1938, p. 174; G. E. F.
Lundell, J. 1. Hofmann, and H. A. Bright, Chemical Analysis of Iron and
Steel, 1931, p. 390.
IV,71. FLUOSILICATE
Discussion. The determination of this anion is of little practical im-
portance. T~e me.t~ods available for its estimat~on w.ill, ho~ever, be out-
lined. Alkah fluoslhcates are decomposed by heatmg wIth sodmm carbonate
solution into a fluoride and silicic acid:
Na 2[SiF 6] + 2Na 2C0 + H 20
3 = 6NaF +H Si0 3
2 + 2C0 2
Insoluble fluosilicates are brought into solution by fusion with four times
the bulk of fusion mixture, and extracting the melt with water. In either
case, the solution is treated with a considerable excess of ammonium carbon-
ate, warmed to 40 C., and, after standing for 12 hours, the precipitated
silicic acid is filtered off, and washed with 2 per cent ammonium carbonate
solution. The filtrate contains a little silicic acid, which may be removed
by shaking with a little fr~shly precipitated cadmium oxide. The fluoride
in the filtrate is determined as described in Section IV, 57.
If an acid solution of a fluosilicate is rendered faintly alkaline with aqueous
sodium hydroxide and then shaken with freshly precipitated cadmium
oxide, all the silicic acid is adsorbed by the suspension. The alkali fluoride
is then estimated in the filtrate.
IV,73. FERRICYANIDE
No satisfactory gravimetric method is available. For volumetric methods,
see Chapter III.
IV,74. NITRITE
No satisfactory gravimetric procedure is available. Volumetric methods
are described in Chapter III.
IV,75. N:J:TRATE
Discussion. The mono-acid base nitron, C20H 16N 4, forms a fairly insoluble
crystalline nitrate, C2oH16N4,HN03 (solubility is 0099 g. per litre at about
20 C.), which can be used for the quantitative estimation of nitrates (see
Section I, 62, I). The sulphate and acetate are soluble so that precipitation
may be made in sulphuric or acetic acid solution. Perchlorates '(008 g.),
iodides (017 g.), thiocyanates (04 g.), chromates (06 g.), chlorates (12 g.),
nitrites (19 g.), bromides (61 g.), ferro cyanides , ferricyanides, oxalates,
and considerable quantities of chlorides interfere, and should be absent.
The figures in parentheses are the approximate solubilities of the nitron salts
in grams per litre at about 20 C.
Determination of nitrate as nitron nitrate. Procedure. The solution
(75-100 ml.) should be neutral and contain about 01 g. of N0 3 . Add
1 ml. of glacial acetic acid or 05 ml. of 2N-sulphuric acid, and heat the
506 Quantitative Inorganic Analysis
solution nearly to the boiling point. Then introduce IO~12 ml. of the
nitron reagent (1), stir, and cool in ice-water for 2 hours. Filter through
a weighed filter-crucible (Gooch, sintered-glass, or porous-porcelain).
Wash with 20~40 m!. of a cold saturated solution of nitron nitrate
added in several portions, and drain the precipitate well after each
washing. Finally, wash twice with 3-ml. portions of ice-cold water.
Dry at 105 0 C. (1 houris usually required), and weigh as C2oH16N4,HNOa.
Note. 1. Prepare the reagent by dissolving 5 g. of nitron in 50 ml. of 5 per
cent acetic acid.
IV,76. CARBONATE
Discussion. The carbonate is decomposed by dilute acid, and either the
loss in weight due to the escape of carbon dioxide determined (indirect
method) or the carbon dioxide evolved is absorbed in a suitable medium
and the increase in weight of the absorbent determined (direct method).
The direct method gives more satisfactory results, and will therefore be
described. The indirect method is often em.
ployed, however, for samples containing reo
latively large amounts of carbonate.
Glass WOOl The decomposition of the carbonate may be
plug
effected with dilute hydrochloric acid, dilute
CaCIZ perchloric acid, or syrupy phosphoric acid.
The last-named acid is perhaps the most con
venient because of its comparative non-vola.
Gla;~u~ool tility and the fact that the reaction can be
more easily controlled than with the other
acids. If dilute hydrochloric acid' is em-
FIG. IV, 76, 1. ployed, a short, water-cooled condenser
should be inserted between the decomposi-
tion flask and the absorption train (see below).
Two absorbents are required, one for water vapour and the other for
carbon dioxide. The absorbents for water vapour which are generally
employed are: (a) anhydrous calcium chloride (14~20 mesh), (b) magnesium
perchlorate trihydrate (" dehydrite "), and (c) anhydrous magnesium per
chlorate (" anhydrone "). Both (b) and (c) are preferable to (a); the former
absorbs about 35 per cent and the latter about 50 per cent of its weight of
water. They are, however, expensive, and anhydrous cal'Cium chloride is
generally employed for ordinary work. The latter usually contains a little
free lime, which will absorb carbon dioxide also; it is essential to saturate
the U-tube containing the calcium chloride with dry carbon dioxide for
several hours and then to displace the carbon dioxide by a current of pure
air. Anhydrous calcium sulphate (" drierite") or anhydrous barium
perchlorate (" dessichlora ") may also be used.
The absorbents for carbon dioxide in general use are: (d) soda lime (this
is available also in the form of self indicating granules, " sofnolite ", or as
" carbosorb " soda lime, which indicate when the absorbent is exhausted),
(e) soda lime-asbestos (the "carbosorb" variety gives a marked colour
change and therefore indicates the degree of exhaustion), and sodium
hydroxide~asbestos (" ascarite "). In all cases the carbon dioxide is
absorbed in accordance with the following equation:
2NaOH + CO = Na COa + H 0
2 2 2
(a) (6)
FIG. IV, 77, 4.
iridium), although cathodes of tantalum are occasionally employed for
the deposition of certain metals. Silver electrodes (Fig. IV, 77, 7, a)
are useful as cathodes for copper and zinc determinations. Numerous
types of electrodes have been employed. . The present tendency is to
use gauze electrodes, particularly for the cathode, because they are
considered to be the most satisfactory. It is probable that the interstices
in the gauze bring about a much better circulation of the electrolyte so
far as conditions at the surface of the electrode are concerned, the
improved circulation serving to reduce any local depletion of the electro-
Gravimetric Analysis 511
lyte that might tend to occur. These gauze electrodes may not be in
the possession of every laboratory, so that other, in some cases less-
expensive, electrodes will be described also.
The simplest apparatus to employ is a platinum dish as cathode and
a circular platinum plate as anode (Fig. IV, 77, 4, a): a circular plati-
num gauze electrode (Fig. IV, 77, 5, e) may also be used. The filter-
flask (Fig. IV, 77, 4, b) is for the removal of the electrolyte after the
electrolysis. L. Classen (1927) gives the following details: diameter of
dish 9 cm.; depth in the centre 42 cm.; capacity about 250 m!.;
weight 35-40 g.; the inside surface should be matted (e.g., by sand
blasting) so that the deposit adheres more easily; surface area for
150 ml. is ca. 100 sq. cm., and for 180 ml. of liquid ca. 130 sq. cm.;
diameter of anode 45 cm.; the electrodes should be used exclusively
a/l
(6)
(aJ (a) (6)
FIG. IV, 77, 6. FIG. IV, 77, 7.
7"
CLASS
TlN-LEAD
ALLOY
COPPER
WIR.E
3" CLASS
ASBESTOS
o
(a) (0) (c)
FIG. IV, 77, 9.
glass stirrer: the stationary anode may then be less robust; furthermore,
the electrical connexions through the chuck (supporting the anode)
are now no longer necessary. The electrodes most widely used with an
independent stirrer are shown in Fig. IV, 77, 12, and are a slight modi-
fication of those described by A. Fischer in 1907; the cathode, which
may also be of the split-cylinder pattern, is provided with two rings
to house a glass tube which fits over the anode stem, thereby giving
excellent insula tion and assisting to locate the stems when employing
* For an excellent account of electrodes suitable for electrochEmical analysis, Eee tl:e
booklet" Platinum Electrodes ", No. 1720 (1949), publi,hed by Johnson, Matthey and
Co., Ltd., Hatton Garden, London, E.C.l; Eee a'so A.S.T.M. Methods of Chemical
Analysis of Metals, 1946, p. 13.
I' s
514 Quantitative Inorganic Analysis
a commercial electrolytic apparatus. Two patterns are manufactured
to this design in different weights.
In unstirred electrolytes, any of the electrodes described above may
be used. It is usual to employ gauze electrodes. When anodic
deposits are not required or if the deposits are small (e.g., if the per-
centage of lead does not exceed 02), a small spiral electrode (Fig.
IV, 77, 5,1) will suffice as the anode.
A mercury cathode is sometimes employed for special operations.
The most important of these is the separation of aluminium from such
metals as iron, manganese, chromium, nickel, cobalt, zinc, molybdenum,
cadmium, copper, tin, bismuth, and lead, which can, under suitable
conditions, be deposited on the mercury. The method is therefore of
FIG. IV, 77, 10. FIG. IV, 77, 11. FIG. IV, 77, 12.
o (a)
Q (b) ~ (e)
FIG. IV, 77, 13.
GD
diameter of the wire.
C. Electrode vessel. Tall-form beakers, without lip, are gpnerally
employed to hold the solution to be electrolysed. These
should be of such size that there is the smallest practicable
volume of liquid between the cathode and the glass. The
apparatus should be so arranged that the beaker can be
easily removed without touching any other part of the
apparatus, and also so that the electrolyte can be warmed, F !G. IV, 77, 14.
if necessary. To prevent loss by spraying, split clock-
glasses with a central hole (Fig. IV, 77, 14) are used for covering the
electrolytic vessel.
516 Quantitative Inorganic Analysis
A form of electrode vessel, which has been employed for rapid electro-
lysis is shown in Fig. IV, 77, 15. At the end of the electrolysis tho
+ solution may be easily drawn off (and used in other de-
terminations, if desired) and the electrodes washed with-
out interrupting the circuit. The disadvantages are:
(i) the vessel cannot be heated easily, and (ii) the liquid
just above the tap does not readily mix with the bulk of
the solution.
D. Stirring. It has already been pointed out (Section
1, 70) that stirring of the electrolytes during electrolysis
reduces considerably the time required for deposition.
The method commonly employed is to rotate the inner
electrode; this is usually made the anode except in lead
determinations (as Pb0 2 ), when it is the cathode. Speed'!
up to 500-1000 r.p.m. are permissible; those usually
employed are 300-600 r.p.m. The rotation is generally
obtained by drive from an electric motor; a device is
always incorporated for varying the speed, for example,
an electrical resistance with a D.C. motor, pulleys, gears,
FIG. IV, 77, 15. etc. Sometimes an independent stirrer is employed, but
this is not generally quite so satisfactory as rotating one of the elec-
trodes. Magnetic stirring is occasionally employed (see Fig. IV, 87, 2).
Many of the commercial apparatuses (see footnote in A) have the
stirring arrangement incorporated
in the main stand. A simple
apparatus, utilising Sand's elec- .
trodes, is shown in Fig. IV, 77, 16.
The inner electrode is attached 7'
through a silver or silver-plated
w
chuck and rubber tubing to a
[ ~ )=t_; t
IV,82. COBALT
Discussion. The determination of cobalt follows along the same lines as
given under Nickel (Section IV, 81). The addition of a little hydrazine
sulphate improves the character of the cathode plate by reducing the
tendency to form an oxide deposit at the anode.
IV,83. SILVER
Discussion. Silver may be determined by electrolysis in nitrate, am-
moniacal, or cyanide solutions. In cyanide solution the silver is present
largely as the complex ion:
[Ag(CN)2]- ~ Ag+ + 2CN-
an excellent plate is obtained, and separation from other elements (e.g.,
copper and lead) may be effected. The cyanide method will be described.
The disadvantage of the electrolytic method is that so many other
clements arc also deposited, either wholly or in part, that a number of
preliminary separations are usually required bdore it can be applied.
For this reason, it is not widely employed.
Procedure. The silver (ca. 02 g.) should be present in solution as
the nitrate. Add pure (e.g., A.R.) potassium cyanide until the pre-
cipitate of silver cyanide is dissolved, and then add an excess such that
about 2 g. of potassium cyanide is present in the solution. Dilute to
100-120 ml. Electrolyse with 02-05 arnp. at 3'7-4'8 volts at 20-
30 C.; about 01 g. of Ag is deposited in 3 hours. Alternatively,
electrolyse with a rotating electrode with 05-1'0 amp. at 25-32 volts;
02 g. of Ag is deposited in 20-25 minutes. Completeness of deposition
is tested for by transferring a few drops of the electrolyte to a test-tube,
acidifying with a little nitric acid, boiling off the hydrocyanic acid
(caution: poisonous), rendering ammoniacal, and adding a few drops
of ammonium sulphide solution; no bJ'own precipitate should be
obtained. The determination is completed as under Copper (Section
IV, 78).
Note. If insoluble silver salts are to be analysed, e.g., chloride, bromide,
io:iide, and oxalate, these may be dissolved directly in the potassium cyanide
solution.
IV,84. ZINC
-
Discussion. Zinc is quantitatively depositcd from an alkaline zincate
solution containing excess of alkali. The proportion of alkali is not of great
importance, provided that it exceeds a miniJllum of 10 molecules of alkali
hydroxide to 1 molecule of zinc salt: it is unnecessary to cmploy a larger
excess of alkali than is required to keep the solution clear during the whole of
the electrolysis. Ammonium salts, if present, must be decomposed by the
addition of excess of caustic alkali and boiling. Chlorides and nitrates inter-
fere; they must be removed, if present, by evaporation to fuming with
sulphuric acid.
Zinc should not be directly deposited on a platinum surface, as it is difficult
to remove it completely (it tends to leave black stains), and upon heating
may alloy with the noble metal. The platinum electrode should be plated
Gravimetric Analysis 525
with copper or, preferably, with silver. Alternatively, a silver-gauze cathode
(as Fig. IV, 77, 7, a) may be used. Cathodes of nickel have also been used,
and are quite satisfactory.
A useful application (If the electrolytic method is in the analysis of alloys
containing aluminium and zinc.
Procedure. For practice in this method, weigh out accurately about
03 g. of A.R. zinc oxide, dissolve it in the minimum volume of dilute
sulphuric acid, add a concentrated solution of 7 g. of A.R. sodium hydr-
oxide in water, stir until the solution is clear, dilute to 125 mI., and
electrolyse, using a copper- or silver-plated platinum cathode or a silver
cathode. For slow electrolysis, use a current of 04-08 amp. at 38-42
volts. For rapid electrolysis (rotating electrode), the current may be
increased up to 5 amps. The metal is more rapidly deposited at about
60 C. When electrolysis is complete, remove the solution without
interrupting the current, wash thoroughly with water, then with alcohol
or acetone, dry at 60-70 C., and weigh. Calculate the percentage of Zn
in the sample.
IV,85. BISMUTH
Discussion. The most satisfactory results are obtained by the use of
controlled potential at the cathode (see Sections IV, 87-88). In chloride
solution, oxalic acid is added as a solvent for the oxychloride and basic
salts, and hydrazine hydrochloride is introduced as a depolariser and also
to prevent the formation of bismuth pent oxide at the anode. The deposition
from sulphate solution takes place in the presence of a high concentration
of sulphuric acid, a hydrazine
,
salt, and at elevated temperatures.
Procedure. From Chloride Solution. For practice in this determin-
ation, use a solution prepared by dissolving 02-025 g. of pure
bismuth in 10 mI. of concentrated hydrochloric acid containing a
small amount of nitric acid. Add 5 g. of oxalic acid, 05 g. of hydrazine
hydrochloride, and dilute to 100 mI. Use Sand's electrodes (Figs.
IV, 77, 8-9) and carry out the determination at 80-85 C. Regulate
the current to give a cathode-saturated calomel electrode potential of
- 015 to - 017 volt. When the current has fallen to a very small value,
adjust the cathode potential in steps of 002 volt to - 025 to - 030
volt.- The determination is complete in 15-20 minutes.
From Sulphate Solution. A solution for practice in the determin-
ation may be prepared by dissolving the metal (0'15-025 g.) in
concentrated sulphuric acid, if necessary by the addition of one-tenth
of the volume of concentrated nitric acid. Cool the solution and dilute
with water so that the resulting test solution, volume about 100 mI.,
contains 20-25 mI. of concentrated sulphuric acid. Add 1 g. of
hydrazine sulphate as depolariser. Heat the solution to 100 C. and
electrolyse, using an initial cathode potential to the saturated calomel
electrode of - 0055 volt. When the current has fallen to a small
value, adjust the cathode potential in three steps to - 015 volt.
Discontinue the electrolysis when the current has fallen to almost zero
at - 015 volt. The determination is complete in 10-30 minutes.
It has been stated that electro-depo'sited bismuth tends to alloy with
platinum; it is therefore advisable to protect the cathode by plating it
with silver from a cyanide solution.
526 Quantitative Inorganic Analysis
IV, 86. Electrolytic separation and determination of copper and
nickel.-
Discussion. This determination has been included at this stage in order
to indicate the use of the electrolytic method in the separation and determina-
tion of metals in simple alloys. More complex alloys require the application
of methods -utilising controlled potential at the cathode; examples of such
separations will be found in Section IV, 89. The theory of simple separations
is discussed in Section I, 69. There are a number of alloys, which include
Monel metal, certain coinage alloys (e.g., American), and" cupro-nickel,"
which are composed principally of copper and nickel, together with small
amounts of iron and manganese and not more than traces of other elements.
These are suitable for practice in electrolytic separation.
The copper is determined in strongly acid solution at a potential not
exceeding 4 volts (above this potential nickel may plate out). The sl"llution
is evaporated to fuming in order to remove excess of nitric acid, the iron
present is precipitated with ammonia solution, and the nickel deposited
from the filtrate after the addition of a large excess of ammonia solution.
The separation of lead and copper by electrolysis is described in Section IV,
91 (analysis of brass).
Silver and copper in silver-copper alloys (silver solder, sterling silver, and
certain coinage alloys) may be separated and determined electrolytically by
dissolving the sample in 1 : 1 or 1 : 2 nitric acid, removing the excess of
nitric acid by evaporation, and then estimating the silver after the addition
of excess of pure potassium cyanide at a voltage not exceeding 15 (Section
IV,83). The residual solution is acidified with nitric acid, the hydrocyanic
acid boiled off, and the copper deposited as detailed in Section IV, 78.
Alternatively, the silver may be deposited from ammoniacal solution (5 ml.
of free concentrated ammonia solution per 100 ml. of solution). Most of the
silver is deposited with a current of 04 amp., a little hydrogen peroxide is
added to oxidise cuprous salts and to re-dissolve any particles of silver not
plated on the electrodes, and the deposition completed at 02 amp. It is
essential that the solution be vigorously stirred during the whole of the esti-
mation. The copper is determined in the residual electrolyte after acidifying
with nitric acid and diluting.
Procedure (analysis of a copper-nickel alloy). Weigh out accurately
about 05 g. of the clean alloy (1) into a 150-m!. beaker, which should
be suitable as an electrolytic vessel. Add a mixture of 10 m!. of water,
1 ml. of concentrated sulphuric acid, and 2 ml. of concentrated nitric
acid to dissolve the alloy. When solution is complete, boil off the
oxides of nitrogen, and dilute to 100 ml. The solution is how ready for
the deposition of copper.
Copper. Proceed as directed in Section IV, 78, and employ either
the slow or rapid method of electrolysis. Wash the copper deposit
thoroughly with water, and keep the solution for the estimation of
iron and nickel.
Iron. Evaporate the solution and washings from which the copper
has been removed on a low-temperature hot-plate as far as possible,
and then heat at a higher temperature until fumes of sulphur trioxide
appear. Cool the residue, and carefuVy add water until the volume is
about 25 ml. Precipitate the small quantity of iron that is now present
in the ferric state by adding to the warm solution about 10 ml. of 1 : 1
ammonia solution in excess. Filter through a small quantitative
filter-paper, and collect the filtrate in a 150-ml. electrolytic beaker (A).
Wash the precipitate three times with water. Place the original
Gravimetric Analysis 527
eaker under the filter; dissolve the precipitate in a little hot 1 : 5
1lphuric acid and wash the paper with water. Precipitate the iron
gain with the same large excess of 1 : 1 ammonia solution, and filter
wough the same paper. Wash the precipitate, and collect the filtrate
nd washings in beaker (A) containing the filtrate and washings from
ile first precipitation. Ignite the ferric hydroxide to ferric oxide, and
'eigh it (Section IV, 8).
Alternatively (since the weight of ferric hydroxide is small), the
'ashed precipitate may be dissolved in dilute hydrochloric acid and the
'on determined colorimetric ally (Section V, 13).
Nickel. Add 15 ml. of concentrated ammonia solution to the
mmoniacal nickel solution, and dilute to 100-120 ml. Carry out the
etermination as detailed in Section IV, 81.
Calculate the percentage of copper, iron, and nickel in the alloy.
Note. 1. Either Ridsdale's " Cupro-Nickel, No. 19" (one of the Analysed
amples for Students) or the Bureau of Analysed Samples" Cupro-Nickel
fo. 180A" (one of the British Chemical standards) is suitable for this
3timation.
When referred to the saturated calomel electrode (EO =' + 0246 volt),
the values are + 0'099, + 0'040, + 0'010, and - 0019 volt respec-
tively. It is clear that for every ten-fold decrease in the concentration
of a univ1'Jent metal ion, the cathode potential becomes + 0,0591/1 volt
more negative; similarly, for a bivalent ion 00591/2 = 00295 volt
more negative, and for a trivalent ion 0'0591/3 = 00197 volt more
negative. Neglecting for the moment the overvoltage at the cathode,
we have here a means of fonowing the change in the concentration of
the metal ion during the electrolysis and, by controlling the potential,
of separating one metal from another lying somewhat higher in the
electromotive series. In order to prevent the cathode potential from
exceeding a predetermined value it is simply necessary to decrease the
potential applied to the cathpde and anode by suitable means. If an
accuracy of 01 per cent (1 part in 103 ) suffices for the analysis, the
applied potential must be decreased by 3 X 0059 = 0177, 3 X 00295
=-=' 0'088, and 3 X 00197 = 0059 volt for univalent, divalent, and
trivalent ions respectively during the analysis.
The optimum potential for a particular electrolysis cannot be cal-
culated with any precision from theoretical principles because of the
variable nature of the overvoltage at the cathode; this value is usually
small, but it must be pointed out that the overvoltage depends upon
the rate of stirring, the current, and the nature of the metal surface.
If the electrode reaction is reversible or nearly so, the potential may
be computed approximately from the Nernst equation; the overvoltage
must be added to this figure. The limiting potential is usually deter-
mined more or less empirically. The most trustworthy procedure is
to determine experimentally the current-cathode potential curve under
exactly the same conditions as will prevail in the proposed estimation.
The optimum conditions for controlled potential with the mercury
cathode can be deduced from polarograms oMained with the dropping-
mercury cathode:. the optimum potential range corresponds to the
diffusion-current plateau in the polarogram (compare Chapter VIII).
In order to separate or separately determine two elements by the
controlled-potential technique, their reduction potentials must differ
by at least 0,15-020 volt, and a somewhat larger difference may be
necessary in unfavourable instances,
When the potential of the cathode is controlled during electrolytic
depositions, the auxiliary electrode is usually connected to the positive
and the cathode to the negative terminal of the valve voltmeter or
high-resistance voltmeter. After the stirring motor has been switched
530 Quantitative Inorganic Analy~i8
. on, the current is adjusted to a suitable value and the cathode-S.C.E.
(or auxiliary electrode) potential is read on the voltmeter. The voltage
is prevented from exceeding this value by adjusting the slider on the
large (current) rheostat (Fig. I, 71, 1) or by manipulating the Variac.
When the current has fallen to about 02 amp., Sand (1940), utilising a
relatively simple apparatus, recommends that the current be increased
until the voltmeter registers an increase of 005 volt; the voltmeter
reading at this value is again maintained constant by adjustment of
the current until the latter has fallen to the previous lowest value. Two
more increases of 005 volt are usually made, the last voltage being
maintained for 3-5 minutes.
Alternatively, using a stirring speed of 600-800 r.p.m., the current is
turned on and the variable resistance or Variac is adjl}.sted until a
current of 2-4 amps. is obtained. When the cathode-saturated
calomel-cell voltage attains the limiting value as indicated by the
valve voltmeter, the external resistance is increased or the Variac
setting is decreased sufficiently to maintain the limiting cathode
potential. Meanwhile the appropriate range of the multi-range am-
meter is brought into circuit. The electrolysis is discontinued when
the current has been reduced to 20-30 mAo Under these experimental
conditions a copper determination, for example, may be completed in
10-15 minutes.
For the separation by controlled potential of metals, such as silver,
which are more noble than, say, bismuth, it would be necessary to
reverse the connexions to the valve voltmeter, and as the metal is
removed, the readings would clearly decrease instead of increasing;
a reversing switch is therefore desirable in the voltmeter circuit.
Finally, attention is directed to the fact that washing and discon-
nexion, when working with controlled potential, are carried out as
already detailed for simple depositions (Section IV, 77E). The motor
should not be stopped before the electrodes are outside the electrolyte,
and the current should not be turned off until the cathode has been
removed.
IV,88. Controlled potential electro-analysis. Apparatus for automatic
control of cathode potential.-The apparatus * enables one to maintain
a constant potential at the cathode at a definite predetermined value
during electro-analysis. The range of D.C. potential available is
0-18 volts when a 2-volt accumulator is employed with the potentio-
meter, but it may be extended, if desired, to 36 volts by using two 2-volt
accumulators in series. The potentiometer is standardised against the
standard Weston cell with the aid of the built-in valve voltmeter. The
current used in the electrolytic cell may vary from a few milliamperes to
10 amps; under normal working conditions the maximum current will
not generally exceed 2-4 amperes. The potential difference between
the cathode and a reference electrode (usually a saturated calomel
half-cell) may be set to about a millivolt and maintained at this value
. automatically. This sensitivity is somewhat higher than is usually
necessary for most applications of controlled-potential electro-analysis:
a variation of 001 volt is generally permissible.
A diagrammatic representation of the set-up of the whole apparatus
is shown in Fig. IV, 88, 1. The operation of the instrument depends
* This apparatus was designed and built by J. F. Palmer with the assistance of C.
Wadsworth under the general direction of the author.
Gravimetric Analysis 531
upon the detection of a D.C. "error voltage" between a fixed cell
(potentiometer, Fig. IV, 88, 7) and the controlled cell (cathode of the
electro-deposition cell and saturated calomel reference electrode).
This "error voltage" is impressed between the vibrating "reed"
of a polarised relay (Fig. IV, 88, 5) and the centre tap of a mu-metal
step-up transformer, the two fixed contacts of the relay being connected
to each end of the primary winding of the transformer. The secondary
winding is connected to the input of a three-stage, resistance-capacity-
coupled voltage amplifier. The output of this amplifier is fed to the
paralleled grids of two 6SN7 valves, the plates (anodes) of which are
connected directly to the secondary of the centre-tapped mains power
transformer (Fig. IV, 88, 5). The valves therefore act as phase-dis-
criminating power amplifiers: the phase relationship between the
amplified puls.e and the voltage of the secondary winding produces a
rectified impulse in the motor winding L2 (Fig. IV, 88, 3). The phase
relationship between this amplified pulse and its counterpart through
MAINS INpUT
+ -
'f,. ~i-+-+,
VARIAC
UNIT
CALOMEL OR REFERENCE
ELECTROLYSIS ELECTRODE
CELL
FIG. IV, 88, 1.
:~"
I :E
I 0
u
:J~
ci -
z I :J
o I 0-
~
!2w I
I V
f-
o r
~
o 10 ~
-' ..........'---------'----'----"------1
:=t
i
5
~. ~ : I
HAINS:' :
INPUT_r";-!-_7-:
; ~
--+t_ __ n_~ ___ J
:
~:
:- 1
MOTOR DIRECTION PLUG TO
CONTROL UNIT (MANUAL) VARIAC UNIT
with condenser 0 4 (Fig. IV, 88,3) when the amplifier unit is plugged into
the Variac unit: this condenser increal3es the torque of the motor to a
satisfactory value when it is under automatic control.
4. Valve voltmeter. The circuit (Fig. IV, 88, 6) is of the Wheatstone-
bridge type: two arms consist of two equal resistances R13 and R14 of
20,000 ohms each, whilst the other two arms are formed by the internal
resistances of two EF39 valves, which flhould possess similar character-
istics. The control grid of one of the valves is earthed. The voltage
to be measured is applied to the control grid of the other valve: this
causes an unbalance in the circuit whi<;h is indicated on the meter M 5'
the deflection being linear to well within 1 per cent. If greater accuracy
is required, a calibration curve must be prepared. The initial balancing
of the bridge circuit (i.e., bringing the meter deflection to zero) is
* This sensitivity refers to an input resistanc!') of 100 ohms (i.e., that of the auxiliary,
e.g., saturated calomel, electrode); it will be SOIllewhat lells for a higher input resistance,
but can easily be restored (if required) to a va1ue of at least one millivolt by the in-
sertion of another stage of amplification in the circuit of Fig. IV, 88, 5.
Gravimetric Analysis 535
controlled by the 2,200 ohms potentiometer V 3 If it is found that the
potentiometer cannot reduce the deflection to zero (due to differences
in the two EF39 valves), a small fixed resistance of about 100 ohms,
placed in one of the cathode leads, will enable the zeroing to be carried
out. Alternatively, one or both of the EF39 valves should be replaced.
The smooth action of the control will be adversely affected if the
resistance of V3 is increased.
The sensitivity of the valve voltmeter is controlled by a two-gang
potentiometer (V4 + V 5 ), each section being of approximately 7,000
ohms resistance. Fine adjustment is provided by the potentiometer
V6 (22,000 ohms). The fixed resistance R 15 and the condenser 0 12
serve to filter out any alternating current in the input voltage.
The selector switch 8 12 permits the use of any of the four ranges
..--------------_H.T.+
R'6
+
RI7
+
RIB
+
R"
L...---J..------------'----J-.--'---.L-_H.T. _
FIG. IV, 88, 6.
(0-05, 0-10, 0-25, and 0-50 volts), the upper three ranges being
pre-set by the potentiometers VA, VB, and Vo; the lowest range is
controlled by the sensitivity controls V 4 + V 5 (coarse) and V 6 (fine).
A chain of high stability resistors R 16 , R 17 , R 1S ' and R 19 is connected
across the input to the valve voltmeter, giving a total input resistance
of 10 megohms. A reversing switch 8 13 is incorporated in the circuit
to provide for change in the polarity of the cathode relative to the
reference electrode.
The high tension (150 volts) is supplied from a stabilised power pack,
whilst the low tension (63 volts) is fed directly from the appropriate
winding on the power pack transformer (Fig. IV, 88, 8).
Prior to installation in the cabinet, the initial calibration of the valve
voltmeter is carried out as follows. The instrument is allowed to
warm up for 10-15 minutes, and a voltage of 0500 volt (e.g., from a
Tinsley low resistance potentiometer) is applied to the external input
with the selector switch 8 15 (Fig. IV, 88, 7) set at EEXT. The sensitivity
536 Quantitative Inorganic Analysis
controls (V4 + V 5) and V 6 are adjusted to give a reading of 0500 volt
with the range selector switch 8 12 (Fig. IV, 88, 6) set at the 0-05 volt
range. The zero is then checked by disconnecting the external voltage,
short-circuiting the external input terminals of the valve voltmeter,
and adjusting the sensitivity control V 6 (fine) if necessary. The range
selector switch 8 12 is now turned to the 0-10 volt range and the
potentiometer VA is adjusted to give a reading of 0500 volt. The
zero should again be checked as before. Once these two proportional
ranges have been adjusted, the two higher ranges may be set with the
aid of the Weston cell. The external voltage is disconnected, the
meter M5 adjusted to read zero, switch 8 12 is retained at the 0-10 volt
range, the selector switch 8 15 is turned to En;PTJT and switch 8 16 to
STD. CELL; V6 is adjusted so that a reading of 1018 volts is obtained
on the meter. The range selector switch 8 12 is then set at 0-25 volts
and the potentiometer VB adjusted to give a reading of 1018 volts;
the zero is again checked by turning the switch 8 16 to D.C. INPUT.
The range selector switch is finally rotated to the 0-50 volts range and
the potentiometer Va adjusted to give a reading of 1018 volts; the
zero is again checked as in the previous calibration. Once the adjust-
ments of the potentiometers VA, VB, and Va have been made and the
ranges checked against the Weston cell, the valve voltmeter may be
assembled in the cabinet. .
The valve voltmeter is calibrated as follows prior to use. The range
selector switch 8 12 is set at the 0-10 volt range, the instrument is
allowed to warm up for 10-15 minutes, and V3 is adjusted so that the
meter M5 reads zero. Switch 8 16 (Fig. IV, 88,7) is set at STD. CELL
and the valve voltmeter input selector switch 8 15 at EIKPUT. The
meter should read 1018 volts. If this is not the case (due to accidental
movement of the calibration controls, variation in the voltage of the
mains, etc.), the zero should again be checked by turning 8 16 to D.C.
INPUT and V6 re-adjusted to give a reading of 1018 volts. It is
important that the leads from the deposition cell to the D.C. INPUT
socket should not be inserted whilst the zero of the meter is being
adjusted; if this connection be made, an unbalance of the voltmeter
may result and a false zero will be obtained. ,
5. Potentiometer. The potentiometer circuit is depicted in Fig.
IV, 88, 7. Seventeen fixed and equal resistances (R20-R36) * give steps
of 01 volt, whilst a variable resistance V 7 prlvides fine adjustment over
a range of 01 volt. The various steps are selected by the eighteen-
way single-pole switch 8 14 , The current is supplied by a 2-volt
accumulator B through terminals brought out on to the panel of the
instrument. The potentiometer is adjusted so that it reads the values
on the dials (0'0-17 volts in steps of 01 volt) with the aid of the
variable resistances VB (coarse) and V g (fine) in conjunction with the
valve voltmeter (Fig. IV, 88, 6).
The valve voltmeter input selector switch 8 15 is set at E poT , and a
high-resistance precision voltmeter (20,000 ohms per volt) is connected
temporarily across the potentiometer, i.e., across the same leads as pass
to the valve voltmeter. t The potentiometer is set at 09 volt (the
* The values of the seventeen resistances were made exactly equal to the resistance
of V 7 The resistance of V 7 was rated as 100 ohms by the manufacturers, but upon
m3asurement its value was found to be 980 ohms.
t ThiR independent check of the valve voltmeter was carried out before the instrument
was finally a8sembled in order to determine the error intro:luced by m3asuring potentials
Gravimetric Analysis 537
setting of maximum resistance), and the calibration controls are
adjusted so that the high-resistance voltmeter reads 0900 volt
precisely; the high-resistance voltmeter is then disconnected. The
zero position of the valve voltmeter is again checked, and the reading
(y volts) corresponding to the potentiometer setting of 09 volt is noted
accurately (the actual reading with the author's instrument was
0895 volts). Henceforth when calibrating the potentiometer, the
calibration controls are adjusted so that a reading of y volts on the
TO ERROR
INPUT ON
AMPLIFIER
EXT. INPUT
STD.
CELL
~UT EINPUT
- +1
D.C.INPUT
TO VALVE
VOLTMETER
and the regulator, are drawing 30 mAo The resistance R37 (fixed) +
VIO (variable) should be arranged so that:
into PI (Fig, IV, 88, 3), and the other hole carried the t~o 'WireS to the
A.C. mains.
MISCELLANEOUS COMPONENTS
NOTES ON WIRING
All connexions were made with IS gauge silvered copper wire except in the
low-tension electrolysis unit, where 15-amp. single-covered cable was used.
The connexions from the electro-deposition cell and the D.C. output ter-
minals on the low-tension unit should also be of 15-amp. wire. Ersin's
multicore solder was used throughout the apparatus.
In the wiring of the valves, the A.C. wires (heater leads) should be twisted
together and kept as far away as possible from the wires carrying the signal
voltages; the latter should be as near the earthed chassis as practicable and
should be screened and of minimum length. The anode leads of one valve
should not be in the vicinity of the control grids of a previous valve, as this
may lead to instability. It is particularly important to prevent hum (50
cycles A.C.) pick-up; operation of the motor could occur from the 50-cyclc
hum (sine wave) as well as from the 50-cycle square-topped wave produced
by the vibrator (Fig. IV, 88, 6) on the appearance of a D.C. "error input."
A mains dial light and holder (Bulgin, D.2S0) may be wired across the
mains lead (Fig. IV, 88, 5) to indicate when the apparatus is switched on.
Similarly, dial lights may be fitted across the terminals 3 and 5 of the six-
pin-socket PI of the Variac unit (Fig. IV, 88, 3), and also across the input
leads of the low-tension D.C. unit (Fig. IV, 88, 2).
The efficiency of the valves may be checked (e.g., when a breakdown occurs)
by inserting a 100-ohm resistance in the cathode leads of all the valves and
then switching a milliammeter (0-10 rnA.) across each resistance in turn
using a nine-way, two-pole selector switch (Bulgin, S.436); the latter will
give an "off" position and a check on eight cathodes. The failure of a
rectifier valve will be apparent by a reduced or zero reading on all valves
supplied by it.
The A.C. ammeter M4 (constituting an additional refinement; visible on
the panel of the amplifier unit, etc., of Fig. IV, 88, 9) is wired in the mains-
input leads immediately following the fuses. This ammeter will record
the total current consumed by the apparatus. It will indicate any overload
such as would be produced, for example, if the mains windings of any of the
transformers burnt out or if one of the U50 rectifier valves developed an
internal short circuit.
Belling and Lee, Ltd., Cambridge Arterial Road, Enfield, Middlesex.
A. F. Bulgin and Co., Ltd., Bye Pass Road, Barking, Essex.
Alec Davis Supplies, Ltd., IS Tottenham Court Road, London, W.I.
Dubilier Condenser Co., Ltd,. Ducon Works, Victoria Road, London, W.3.
Erie Resistors, Ltd., Beevor Road, Great Yarmouth.
Alfred Imhof, Ltd., 112-116 New Oxford Street, London, W.C.I.
Measuring Instruments (Pullin), Ltd., Winchester Street, Acton, London,
W.3.
l\LR. Supplies, Ltd., 6S New Oxford Street, London, W.C.I.
Multicore Solders, Ltd., Mellier House, Albemarle Street, London, W.I.
Gravimetric Analysis 545
Reliance Manufacturing Co., Ltd., Sutherland Road, Higham Hill,
Walthamstow, London, E.17.
Dr. G. A. V. Sowter, loB Head Street, Colchester, Essex.
Standard Telephone and Cables, Ltd., Cables Transmission Systems,
North'Woolwich, London, E.16.
Webb's Radio, Ltd., Soho Street, Oxford Street, London, W.l.
Yaxley switches, supplied by British N.S.F., Ltd., 9 Stratford Place,
London, W.l.
Zenith Electric Co., Ltd., Villiers Road, Willesden Green, London, N.W.2.
IV, 89. Determination of metals in alloys using controlled potential of
the cathode.-A. Copper in bronze. Weigh out accurately 05-10 g. of
the bronze,* add 10 ml. of concentrated hydrochloric acid, heat, and
introduce concentrated nitric acid dropwise until the alloy just passes
into solution. Avoid an excess of nitric acid. When the sample has
dissolved, add 20 ml. of concentrated hydrochloric acid and 4 g. of
hydroxylamine hydrochloride, and heat the solution just below the
boiling point until the dark-green colour becomes much lighter, indicat-
ing considerable reduction to the chlorocuprous complex ion. Dilute
the solution to 200-250 mI., and electrolyse with vigorous stirring,
using a saturated calomel auxiliary electrode and a limiting cathode
potential of - 035 volt, i.e., the reading of the valve voltmeter
should be 0'35 volt. [If the assembly for automatic cathode potential
control is used, set the apparatus to limit the cathode-calomel voltage
to 0'35 volt; electro-deposition will then proceed automatically.] The
auxiliary electrode of Fig. IV, 87, I, may be used, with the tip placed
outside and as close as possible to the cathode cylinder at about its
middle. Alternatively, a 6-mm. tube filled with a 3 per cent agar solution
in saturated potassium chloride solution may be employed as. a salt
bridge; the tip of the salt bridge is similarly placed relative to the
cathode. The initial value of the current should be 2-5 amps. so that
the cathode potential at first quickly acquires a value of at least - 030
volt. Copper may not deposit for several minutes after the electro-
analysis is commenced, and indeed the saturated calomel electrode may
first be negative to the cathode: copper will commence to plate out when
the cathode potential is about - 02 volt. Wash down the walls of the
beaker several times during the electrolysis. Continue the electro-
analysis until the current has decreased to about 003 amp. Complete
the determination in the usual manner, removing the electrolyte and
washing off the cathode before turning off the current. Wash the de-
posit of copper well with water, and dry at a temperature not ex'ceeding
0
100 C. for 10 minutes.
Calculate the percentage of copper in the bronze.
B. Copper in copper-base and tin-base alloys. The procedure to be
described is applicable to the determination of copper in copper-base
and tin-base alloys; it may be applied in the presence of lead, tin,
antimony, zinc, and various other elements commonly present in these
alloys, but bismuth and silver interfere and are co-deposited with the
copper. Brasses and bronzes may also be analysed by this method.
The copper is deposited at controlled potential from an acidic tartrate
solution.
* Either Ridsdale's " Gunmetal, No. 6e " (one of the Analysed Samples for Students)
or the Bureau of Analysed Samples" Bronze, No. 207C " (one of the British Chemical
Standards) is suitable for practice in this determination.
T
546 Quantitative Inorganic Analysis
Weigh out accurately a 05-20 g. sample of the alloy * into a covered
250- or 400-mI. beaker, and dissolve it in a warm mixture of 8 mI. of
concentrated hydrochloric acid and 2 ml. of concentrated nitric acid.
Introduce the nitric acid dropwise as required. Boil the solution very
gently for a minute or two to remove most of the oxides of nitrogen and
chlorine. Then add 100 mI. of a solution containing 23 g. of pure
sodium tartrate dihydrate, 1 g. of urea, or, better, 05 g. of sulphamic
acid (to remove oxides of nitrogen), and 10 ml. of 5N-sodium hydroxide
solution.t Dilute the solution to about 200 ml., introduce 1-2 g. of
hydroxylamine hydrochloride as an anodic depolariser, and electrolyse,
whilst stirring efficiently, with a cathode potential relative to the
saturated calomel electrode at - 036 002 volt. The automatic
cathode control potential apparatus, set at 0'35 volt, is recommended.
The initial current is about 3 amps. and drops to a few milliamperes in
about 60 minutes. Lower the beaker away from the platinum-gauze
electrodes, wash the cathode with a little water, then twice with pure
acetone, dry for 3 minutes at 70 C., and weigh after cooling in air for
at least 20 minutes.
If the proportion of lead in the alloy is small (::} 5-10 per cent) and,
provided it does not separate as lead hydrogen tartrate in the prepara-
tion of the solution, it may be determined by a further application of
controlled potential electro-analysis. After the copper deposit has
been weighed, replace the copper-placed cathode in the solution and
electrolyse at a potential of - 055 to - 060 volt VS. S.C.E. Weigh
the lead deposit on the cathode after completing the determination in
the usual way. No lead dioxide is deposited on the anode, but the
results are 2-3 per cent low, due probably to the partial re-solution of
the lead during the washing process.
Calculate the percentage of copper in the alloy.
C. Antimony, copper, lead, and tin in bearing metal. Weigh out
accurately 02-04 g. of the alloy t (as drillings or fine filings) into a
small beaker. Dissolve the alloy by warming with a mixture of 10 ml.
of concentrated hydrochloric acid, 10 ml. of water, and 1 g. of ammon-
ium chloride (the last-named to minimise the loss of tin as the tetra-
chloride). Complete solution may be hastened by the addition, drop
by drop, of a saturated solution of potassium chlorate. When all the
alloy has dissolved, boil off the excess of chlorine, add 5 ml. of concen-
trated hydrochloric acid, dilute to 150 mI., and then add 1 g. of hydra-
zine hydrochloride. Electrolyse at 70-75 C., limiting the potential to
- 04 volt relative to a saturated calomel electrode; the electrodes
depicted in Fig. IV, 77, 9, or in Fig. IV, 77, 12, may be employed.
Copper and antimony are deposited together. After 15-20 minutes
(when the current has fallen to a low value), flush out the liquid in
* Any of the following may be used. Copper-base alloys: Ridsdale's" Gunmetal,
No. 6e" or "Phosphor bronze, No.7"; Bureau of Analysed Samples' " Bronze, No.
207C" or "Phosphor bronze, No. 183A "; U.S. Bureau of Standards, " Ounce Metal,
No. 124b" or "Phosphor bronze, No. 63b." Tin-base alloys: Ridsdale's "White
Metal No. 8b"; Bureau of Analysed Samples, "White Metal, No. 178B"; U.S.
Bureau of Standards, "Tin-base bearing metal, No. 54c."
t If lead hydrogen tartrate separates at this stage, filter the solution before finally
diluting to 200 m!.
t Either Ridsdale's "White Metal, No. 8b" (one of the Analysed S::tmples for
Students) or the British Chemical Standard" White Metal, No. 178B " is satisfactory
for practice in this analysis.
The current is employed not only for the deposition of the antimony but also for
the reduction of stannic to stannous ions. This reduction is catalysed by metallic
Gravimetric Analysis 547
the tip of the reference electrode vessel (compare Fig. IV, 67, 1) into
the electrolysis beaker and continue the electrolysis for a further 5-10
minutes. Dry and weigh the copper-antimony deposit on the cathode.
Separate the copper and antimony by dissolving the deposit in a
mixture of 5 mI. of concentrated nitric acid, 5 mI. of 40 per cent hydro-
fluoric acid, and 10 mI. of water: boil off the oxides of nitrogen, dilute
to 150 mI., and add dropwise a solution of potassium dichromate until
the liquid is distinctly yellow. Deposit the copper by electro lysing the
solution at room temperature and limiting the cathode-S.C.E. potential
to - 04 volt. Evaluate the weight of antimony by difference.
To the solution from which the copper and antimony have been
, separated as above, add 1 g .. of hydrazine hydrochloride. Electrolyse
the solution at room temperature, limiting the cathode-S.C.E. potential
to -'- 07 volt. The lead and tin are deposited together. Dissolve the
deposit in a mixture of 15 mI. of concentrated nitric acid, 5 mL of
concentrated hydrofluoric acid, and 15 ml. of water, and boil off the
oxides of nitrogen. For high-lead alloys (about 25 per cent of lead),
dilute to 150 mI., and deposit the lead as peroxide by electrolysing at
90-95 C. for 20 minutes with a current of 6-6'5 amps. With low-
lead alloys, add 20 mI. of a standard 05 per cent solution of lead (as
nitrate), dilute to 150 ml., and electrolyse as before. Weigh the deposit
of lead dioxide. Calculate the weight of lead, using the factor 0864
for Pb (Pb0 2 ; if lead nitrate solution was added, deduct the weight of
lead which was introduced prior to the electrolysis. Obtain the weight
of tin by difference.
Calculate the proportions of Sb, Cu, Pb, and Sn in the alloy.
D. Copper, lead, tin, and zinc in brass or bronze. Dissolve 02-04 g.,
accurately weighed, of the alloy * in a mixture of 10 mL of concentrated
hydrochloric acid, 2 mL of concentrated nitric acid, 10 mI. of water,
and 1 g. of ammonium chloride. Add a further 5 mL of concentrated
hydrochloric acid, dilute to 150 mI., introduce 1 g. of hydrazine hydro-
chloride and electrolyse for 20 minutes at 50 C., limiting the cathode
potential to - 04 volt relative to a saturated calomel electrode. Use
an initial current of 3-4 amps.; this falls rapidly to about 01 amp.
All the copper is thus deposited, together with any arsenic which may
be present. To free the copper from the arsenic, dissolve the deposit
in a mixture of 5 mL of concentrated sulphuric acid, 5 ml. of concen-
trated nitric acid and 10 ml. of water. Boil off oxides of nitrogen,
dilute the solution to 150 mI., and electrolyse for 20 minutes at room
temperature at a cathode potential of - 04 volt VS. S.C.E.: copper
alone is now deposited.
Deposit the tin and lead from the original solution (from which the
copper has been removed) and subsequently separate them as described
under C.
Oxidise the solution remaining after the removal of the tin and lead
by boiling with a little bromine water until colourless. Add concen-
trated ammonia solution until the solution is just alkaline to phenol-
phthalein, heat to the boiling point, and filter off any small precipitate
antimony, and hence, after the cathode has become covered with this element, a
considerable increase in current takes place. The reduction must be allowed to proceed
until a residual current of about 03 amp. has been in operation for about 10 minutes.
* Ridsdale's "Brass, No. 5e" or "Phosphor Bronze, No.7" (Analysed Samples
for Students) or the British Chemical Standard" Bronze, No. 207C" may be used for
practice in this separation.
548 Quantitative Inorganic Analysis
of ferric hydroxide. This precipitate may be dissolved in dilute
hydrochloric acid and the iron determined colorimetrically. Cool the
filtrate, add 10 ml. of concentrated ammonia solution and 10 m!. of
10 per cent potassium cyanide solution. Electrolyse for 20 minutes at
. room temperature with a current of 3 amps. Weigh the deposit of zinc.
Finally, calculate the percentage of Cu, Pb, Sn, and Zn in the alloy.
Allow to cool in a stream of carbon dioxide, and then titrate the stannous
tin with standard iodine solution (Section III, 116, Procedure B). From the
volume of standard iodine solution required, calculate the percentage of tin.
For the determination of the other metals, treat another sample of the
alloy with 1 : 1 nitric acid, etc., and dissolve the impure metastannic acid in
a mixture of concentrated sulphuric acid and sodium sulphate as above.
Transfer the mixture quantitatively to a beaker, treat cautiously with excess
of sodium hydroxide solution followed by excess of sodium sul,(lhide, and
digest for some time. The tin thus passes into solution as sodium thio-
,;tannate, Na 2SnS 3 , and the sulphides of the other metals (e.g. iron, copper,
zinc, etc.) are precipitated. Allow to cool, dilute somewhat, and filter.
Dissolve the residue in hot 1 : 2 nitric acid, and add the solution to the
main filtrate for the estimation of the other metals.
ANALYSIS OF SOLDER
Discussion. Ordinary solder is an alloy of approximately 3 parts of lead
and 2 parts of tin, but it usually contains also from 1-3 per cent of antimony
as impurity. When such an alloy is disintegrated by nitric acid, the insol-
uble residue consists of metastannic acid and antimonic acid, together with
some co-precipitated lead compound. The ignited residue will consist of
564 Quantitative Inorganic Analysis
Sn0 2 + Sb 2 0 4 + PbO. The amount of lead present in the residue is most
simply determined by the ammonium iodide volatilisation method (Section
IV, 22A); the tin and antimony are volatilised as the iodides, and the lead
remains behind as a mixture of oxyiodide and oxide. The residue in the
crucible is treated with 2-3 m!. of concentrated nitric acid (a Main-Smith
crucible is very suitable for this process), evaporated to dryness on the hot-
plate, the nitrate cautiously decomposed, and finally ignited to oxide at a
low red heat. The loss in weight gives (8n02 + 8b 2 0 4 ). The tin may be
determined as in Method C, SectiolllV, 92 (antimony does not interfere with
this process), and the antimony obtained by difference. The residual PbO
in the crucible may be dissolved in a little concentrated hydrochloric or nitric
acid, and added to the main filtrate from the metastannic acid. The lead
is determined as sulphate (Section IV, 14A) or as chromate (Section lV,
14B); in the latter case, about 12 g. of sodium acetate are added to replace
the free nitric acid by acetic acid.
An alternative procedure is to transfer the impure meta stannic acid pre-
cipitate and filter-paper, preferably dried at 100 C., to a Kjeldahl flask, add
a mixture of 12 ml. of concentrated sulphuric acid and 5 g. of potassium
hydrogen sulphate, and boil gently until the organic matter is destroyed.
The carbonaceous matter from the filter-paper reduces the antimony to
SbHI The mixture is evaporated to fumes of sulphur trioxide, allowed to
cool, cautiously transferred quantitatively to a conical flask with the aid of
about 50 m!. of water, 5 mI. concentrated hydrochloric acid is added, cooled
to 10 C., and titrated with standard OlN-potassium permanganate (see
Section III, 117) :
5Sb+++ + 2Mn0 + 12H 0
4- 2 = 5H 3Sb0 4 + 2Mn++ + 9H+
The percentage of antimony can then be calculated. Excess of concentrated
hydrochloric acid is then added, followed by 2-3 g. of pure lead, and the
mixture boiled gently in an atmosphere of carbon dioxide (see Method C
in Section IV, 92). The quadrivalent tin is reduced by the lead to the bi-
valent state, and the antimony is precipitated as the metal. The stannous
tin is titrated with standard OIN-iodine, and from the volume of the latter
required the percentage of tin may be calculated (Section III, 117).
The procedure is much simplified jf antimony is absent, as in the case of a
pure solder or a pure lead-tin alloy. Such alloys are available commercially,
and are useful for practice in the quantitative separation and determination
of lead and tin. Here the amount of lead oxide present in the impure stannic
oxide may be determined either by the ammonium iodide process or by the
sodium carbonate-sulphur fusion process (Section IV, 91 (a)). The lead is
uetermined in the filtrate from the impure metastannic acid, to which the
small amount of recovered lead lIas been added, as the sulphate.
Analysis of pure solder or a pure lead-tin alloy. Procedure. Weigh
out accurately about 05 g. of the finely divided alloy (turnings, drillings,
etc.) (1) into a 150-200-ml. beaker, and cover with a clock-glass or
Fisher" speedyvap "cover. Add 5 ml. of water, followed by 15 mL
of concentrated nitric acid: keep the beaker covered during the ensuing
violent reaction. When the vigorous reaction is over, evaporate on a
water-bath to a volume of about 5 mI., but not to dryness. Dilute
to 50 mI., heat on a water-bath for 10-15 minutes, then add one What-
man accelerator (or half of an ashless tablet), and stir. Filter through a
Whatman No. 42 or 542 paper, and collect the filtrate in a 250-
400-ml. beaker. Wash the precipitate at least ten times with 1 per
cent nitric acid. Keep the filtrate and washings for the determination
of lead. Fold up the filter-paper and precipitate and place it in a
Gravimetric Analysis 565
weighed porcelain crucible (best in a Main-Smith crucible), and com-
plete the estimation as described for tin in Section IV, 91 (a). Weigh
the impure stannic oxide. Add to the latter about fifteen times its
weight of powdered ammonium iodide, 'and mix the two in the crucible
intimately by means of a small spatula. Heat the crucible in an electric
crucible or muffle furnace at 425-475 C. for 15 minutes or until no
further fumes are evolved. Allow the crucible to cool, remove it, and
add 2-3 ml. of concentrated nitric acid. Evltporate gently to dryness,
and cautiously decompose the residual nitrate over a small flame.
Then ignite at a low red heat to constant weight. The loss in weight
gives the weight of pure stannic oxide present in the residue. Calculate
the percentage of tin.
Dissolve the residue in the crucible by digestion with a few mI. of
concentrated hydrochloric acid, and add it to the filtrate and washings
from the metastannic acid. Add 7-8 ml. of concentrated sulphuric
acid, and evaporate the solution carefully (e.g., on a low-temperature
hot-plate) until white fumes of sulphur trioxide are freely evolved.
Complete the determination of lead as sulphate according to the pro-
cedure given for lead in Section IV, 91 (b) (Method A). Calculate the
percentage of lead.
Note. 1. Ridsdale's "Solder, No. He" (one of the Analysed Samples for
Students) is an almost pure lead-tin alloy, and is suitable for this analysis.
Hydrazoic acid, derived from the slight excess of sodium azide, is very
poisonous and also very volatile.It is therefore readily removed by boiling
for a few minutes in the fume cupboard.
7. The permanganic acid is also reduced by heating with hydrochloric
acid:
+
2HMn0 4 + 14HCl = 2MnC1 2 5C12 8H 20 +
Boiling removes the chlorine formed in the reaction. The precipitated silver
572 Quantitative Inorganic Analysis
chloride acts as a catalyst in this reduction; it has no effect upon the esti-
mation and may be left in the solution.
S. 2H zCr0 4 + 6H zS04 + 6FeS0 4 = Crz(S04)s + 3Fe 2 (S04)a + 8HzO
2HV0 3 + 3H zS04 + 2FeS0 4 = 2(VO)S04 + Fe 2 (S04)3 + 4H 20
9. In the back titration with permanganate solution, the reduced vanadium
is re-oxidised :
2KMn04 + 1O(VO)S04 + 22H 0 2 = K 2S0 4 + 2MnS0 4 + IOH 3V0 4 + 7H 2S04
as is also the excess of ferrous solution. It is therefore clear that the sale
function of the permanganate solution is to react with the excess of ferrous
iron and of the vanadium that has been reduced, and consequently if the
permanganate and ferrous solutions are of equal normality, the difference
between the volumes used represents the volume of ferrous ammonium
sulphate solution required to reduce the chromic acid formed from the
chromium present in the sample.
Method 2. Weigh out accurately about 02 g. of ferro-chromium
(10) into a tall 600-mi. beaker, add 20 mi. of concentrated hydrochloric
acid, cover with a clock-glass, and heat for 15 minutes. Add 20-25 mI.
of pure 60-70 per cent perchloric acid (DANGER, see Section IV, '70),
and boil for 30 minutes after the hydrochloric acid has been expelled.
Cool somewhat, add a few ml. of water to dissolve the chromium trioxide,
and re-oxidise by boiling for 15 minutes after the water is expelled.
If any undissolved particles of metal remain, pour off most of the solu-
tion, add a few mL of 60-70 per cent perchloric acid to the rel'lidue,
and boil until solution is complete. Add the main decanted liquid,
evaporate off the water, and boil for 5 minutes. Cool somewhat, add
an equal volume of water, and boil for 3 minutes to remove chlorine.
Cool, dilute to 200 mI., add excess of O'IN-ferrous ammonium sulphate,
and titrate back the excess of the latter with standard OIN -potassium
permanganate, allowing 1 minute for the end point.
Note. 10. The Bureau of Analysed Samples" Ferro-Chromium, No. 203"
(one of the British Chemical Standards) is suitable for this estimation. If a
Cr-V steel is used, weigh out accurately about 2 g., and dissolve it directly in
20-25 ml. of 60-70 per cent perchloric acid. With ferro-chromium, the
chromium trioxide initially formed tends to cover the particles of ferro-
chromium and thus prevent complete oxidation.
H. Vanadium. The determination of this element is most often
required for chromium-vanadium steels; two methods will be de-
scribed.
Procedure A. The steel is dissolved and treated exactly as in G
(Method 1) for the estimation of chromium in chromium-vanadium
steel until the solution has been titrated with standard O'IN -potassium
permanganate. Then proceed as follows.
Add a moderate excess of OIN-ferrous ammonium sulphate (ca.
10 mI., but note exact volume) (1) to the cold solution. Then introduce
S ml. of a freshly prepared 15 per cent ammonium persulphate solution,
and stir for 1 minute to oxidise the excess of ferrous salt (2). Titrate
with standard O'IN -potassium permanganate until a pink colour
persists for I minute after stirring (3). Calculate the percentage of
vanadium in the alloy.
Gravimetric Analysis 573
Notes. 1. The excess of ferrous solution reduces the vanadium to the
quadrivalent state:
2HV0 3 + 3H S04 + 2FeS0 4 =
2 2(VO)S04 + Fe (S04)3 + 4H 0
2 2
,
Gravimetric Analysis 585
chloric acid, and precipitate the calcium by adding slowly to the boiling
solution 50 mI. of a hot 4 per cent solution of ammonium oxalate,
followed by 1 : 10 ammonia solution until the solution is neutral or
slightly alkaline (to methyl red). Test for complete precipitation by
adding a little more of the oxalate solution. Allow the precipitate to
settle for an hour. Filter off the precipitate, and wash it two or three
times with a cold, 01 per cent ammonium oxalate solution. Set aside
the filtrate (iii). Place the original beaker under the funnel, dissolve
the precipitate in 25-50 ml. of hot 1 : 9 hydrochloric acid, and wash the
paper with hot water.* Dilute to 100 mI., if necessary, add 5 mI. of
the 4 per cent ammonium oxalate solution, boil, then add ammonia
solution dropwise until the solution is just alkaline. Set aside for 1
hour, thus allowing the precipitate to settle. Either of two procedures
may now be used according as to whether the precipitate is to be weighed
as calcium carbonate or as calcium oxide.
Weighing as calcium carbonate. Filter the precipitate through a
weighed porous-porcelain crucible (previously heated at 500 C.), wash
with a 01 per cent ammonium oxalate solution until free from chloride
(ca. 50 ml.; acidify with dilute nitric acid before testing for chloride).
Mix the filtrate and washings (iii') with that from the first precipitation
(iii), and reserve the liquid (iv). Dry the crucible and contents at
110 C. for 30-60 minutes (the composition will approximate to
CaC2 0 4 ,H2 0), and then place it in an electric muffle furnace regulated.
to within 25 of 500 C. Heat for 1-2 hours and weigh as CaC0 3
Repeat the heating to confirm that constant weight has been attained.
Calculate the percentage of CaO in the sample.
Weighing as calcium oxide. Filter the precipitate through a quantita-
tive filter-paper and wash it with a 01 per cent ammonium oxalate
solution until free from chloride (ca. 50 mI.). Mix the filtrate and
washings (iii') with the previous one (iii), and reserve the liquid (iv).
Dry the paper and precipitate, and ignite in a platinum crucible to
constant weight. Weigh as CaO, following the procedure of Section
IV. 10. Calculate the percentage of CaO present in the sample.
Note. The urea hydrolysis m/thod (Section III, 154), which is superior to
that given above, may be used for the precipitation of calcium as oxalate.
A better separation from magnesium results. If the proportion of magnesium
is relatively high, a second precipitation must be made. The calcium
oxalate may be titrated with OIN-potassium permanganate, or it may be
weighed as CaC03
E. Magnesium oxide. The combined filtrates (iv~ contain excess of
oxalate ion and large amounts of ammonium salts; these, as already
pointed out (Section IV. 11), cause the results for magne~ium, when
precipitated as magnesium ammonium phosphate, to be high. This
error may be avoided by double precipitation or by the removal of the
interfering elements. In the latter procedure any ~ilica which may be
present is also removed. By oxidation of the hot solution with nitric
acid in the presence of chloride ions, oxalate is oxidised to carbon
* If difficulty is experienced in dissolving the precipitate directly on the filter, wash
as much as possible of the precipitate into the original beaker, and dissolve the small
amount of the precipitate adhering to the paper by pouring hot 1 : 9 hydrochloric acid
repeatedly through the filter. Then add a drop of methy 1 red, heat until the precipitate
has dissolved, adding more dilute hydrochloric acid if necessary.
586 Quantitative Inorganic Analysis
dioxide and water, and the ammonium salts principally to nitrous
oxide, nitrogen, and water. Both methods will be described.
Method 1. Acidify the filtrate (iv) from the determination of calcium,
and evaporate to 300 ml. Cool, add a few drops of methyl-red indi-
cator, followed by 20 mI. of freshly prepared ammonium phosphate
reagent (25 g. of A.R. (NH4)2HP04 in 100 ml. of water). Then add
pure concentrated ammonia solution slowly whilst stirring the solution
vigorously until the indicator turns yellow; continue the stirring for
5 minutes, keeping the solution alkaline by the addition of more
ammonia solution if necessary, and finally add 10 ml. of concentrated
ammonia solution in excess (i.e., approximately one-thirteenth of the
volume of the solution). Allow the solution to stand for at least 4
hours, but preferably overnight. Filter off the precipitate and wash it
two or three times with 1 : 20 ammonia solution: discard the filtrate.
Place the beaker under the funnel, and dissolve the precipitate in
25-50 mi. of hot 1 : 10 hydrochloric acid. Add 02-0'3 g. of (NH4)2HP04'
and precipitate the magnesium as before in a volume of 150 ml.
Allow to stand overnight, filter off the precipitate, and wash it with
cold 1 : 20 ammonia solution until free from chloride. Complete the
determination as described in Section IV, 11, and weigh a,:; magnesium
ammonium phosphate hexahydrate or as magnesium pyrophosphate.
Calculate the percentage of MgO present.
Method 2. To the combined filtrates (iv) from the calcium estima-
tion, add 50 ml. of concentrated nitric acid, and evaporate carefully to
dryness on a steam-bath or upon a low-temperature hot-plate. Only a
small residue (largely magnesium salts) should remain. Add 2-3 mi.
of concentrated hydrochloric acid and 20 ml. of water, warm the
mixture for a few minutes until the solid has dissolved; if a little silica
remains, filter it through a small paper and wash the residue thoroughly.
Determine the magnesium in the filtrate, after diluting to 150 mI., as in
Method 1; only one precipitation of magnesium ammonium phosphate
is necessary in this case. Calculate the percentage of MgO present.
F. Carbon dioxide. Follow the procedure given in Section IV, 76,
using 05-0,6 g., accurately weighed, of the sample. Calculate the
percentage of carbon dioxide present in the mineral.
Additional determinations. It is sometimes required to estimate the
iron content of the original mineral. As a first approximation we may
assume that the" combined oxides" are composed of Fe 20 3 +A1 2 0 3 .
This is not strictly true, as Ti0 2 and P 20 5 (as metallic phosphates) may
be present, but the error introduced by making this assumption is
usually smaU. The Fe20 3 may be determined directly as detailed
below, and the A1 20 3 may then be obtained by difference. The Al 20 3
may be written, if desired, as A1 20 3 (+ Ti0 2 + P 2 0 5 , etc.), if the
constituents inside the parentheses are knmvn to be present. Alter-
natively, the alumina content may be determined directly with 8-
hydroxyquinoline (for details, see Section IV, 99, C1; this procedure
applies in the presence of titanium).
G. Ferric oxide. The impure silica (B) may, and usually does,
contain a little of the mixed oxides. Treat the impure silica, contained
in a platinum crucible, with 05 mi. of concentrated sulphuric acid and
2-3 ml. of A.R. hydrofluoric acid, evaporate the whole cautiously, and
ignite (see Section IV, 70A); the loss in weight gives the amount of
pure silica present. Fuse the residue with 3-4 g. of A.R. anhydrous
Gravimetric Analysis . 587
sodium carbonate, dissolve the melt cautiously in dilute hydrochloric
acid, boil, then precipitate with ammonia solution as detailed in C.
Filter off the precipitate, re-dissolve it in dilute hydrochloric acid,
and again precipitate with ammonia solution. Filter the latter pre-
cipitate through a small filter-paper, and transfer the paper and pre-
cipitate to the original (platinum) crucible containing the " combined
oxides," and ignite in the usual manner. It is evident that if only a
small residue is obtained after treatment with sulphuric and hydrofluoric
acids, the sodium carbonate fusion is unnecessary except for the most
accurate work.
Add 5-7 g. of pure anhydrous potassium pyrosulphate to the plati-
num crucible containing the ignited mixed oxides, and heat slightly
above the melting point of the pyrosulphate; keep the crucible covered.
After about 20 minutes raise the temperature slowly until eventually
the bottom is at low redness and no dark particles are visible (ca. 1
hour): there must be no spattering. Allow the crucible to cool,
place it in a 250-400-ml. beaker, add 100 ml. of water and 3 ml.
concentrated sulphuric acid, and warm until all the solid has dissolved
with the exception of a few flakes of silica. Remove the crucible with a
glass rod and wash it thoroughly with water. Filter off the silica on a
small filter-paper, and collect the filtrate in a 350-ml. conical flask;
wash the paper thoroughly with hot water. Reduce the solution in a
Jones or cadmium reductor (Sections II, 39, and III, 51B) or with
stannous chloride (Section III, 51A) * and determine the resultant
ferrous iron by titration with standard O'IN-potassium permanganate.
Calculate the percentage of Fe 2 0 3' and by subtracting the weight of the
latter from that of the" combined oxides," evaluate the percentage of
" AI 2 0 3 ."
H. Alternative procedur, for the determination of calcium and
magnesium (molybdate me'thod). The procedure given in D and E
involving double precipitation of the calcium as oxalate, followed by
double precipitation of the magnesium as the ammonium phosphate,
is accurate but time-consuming, The following method is rapid, and
is based upon the comparative insolubility of calcium (also strontium
and barium) molybdate, and the solubilit.f of magnesium molybdate
under the given experimental conditions (pH> 7). The results are
satisfactory for a Mg/Ca ratio of 5/1, but the concentration of the
magnesium must be less than OIN, which may be achieved by dilution.
If the magnesium-ion concentration exceeds O'IN, the precipitate must
be dissolved in hydrochloric acid and the calcium re-precipitated.
Treat the neutral solution ofcalcium and magnesium salts (volume
reduced by evaporation to, say, 40-50 ml.) with excess of the ammon-
ium or sodium molybdate reagent (1). The latter should be added at
the rate of one drop per second until excess is present (2); a moderate
excess of the reagent is not harmful. If the rate of addition is exceeded
or if a stirring-rod is used, the precipitate may adhere tenaciously to
the glass and will require a rubber" policeman" for its removal. Ad-
just the pH of the solution to about 7-8 (methyl-red indicator) by the
addition of filtered ammonia solution. Boil until the supernatant
* Titanium (IV) will be reduced in the .Tones or cadmium reductor to titanium (III),
which will, of course, react with the potassium permanganate_ solution. The titanium
content may be determined colorimetrically (Section V, 15) in an aliquot portion of the
solution prepared from the pyrosulphate melt, and an appropriate correction made.
588 Quantitative Inorganic Analysis
liquid is perfectly clear (about 15 minutes), and allow to stand un~il
cold (30-40 minutes). Filter through a weighed porous-porcelam
filter-crucible, wash with a minimum volume of hot water, dry at
130 0 C. for 30 minutes, ignite upon a crucible-ignition dish or in a larger
crucible (Fig. II, 31, 4) or at 700 0 C. to constant weight. Weigh as
CaMoO 4' and calculate the percentage of CaO present in the sample.
Concentrate the filtrate and washings to about 125 ml. and pre-
cipitate the magnesium as magnesium ammonium phosphate in the
usual way. Weigh as MgNH 4P0 4 ,6H 2 0 or as Mg 2P 20 7 , and calculate
the percentage of MgO present. The excess of alkali molybdate does
not interfere.
Notes. 1. The ammonium molybdate reagent is prepared by dissolving
35 g. of A.R. ammonium paramolybdate and 96 g. of A.R. ammonium
nitrate in 40 ml. of 6N-ammonium hydroxide solution, and diluting to 1
litre. Another method is given in Section IV, 18A.
The sodium molybdate reagent is prepared by dissolving 50 g. of A.R.
sodium molybdate (Na 2Mo0 4 ) in 1 litre of water.
Both reagents should be acidified to pH 4 by the addition of hydrochloric
acid in order to reduce the absorption of carbon dioxide from the atmosphere.
2. To detect excess of the reagent, use the solution adjusted to the correct
pH and which has been boiled for 10 minutes. Allow to settle, remove a
drop of the supernatant liquid, and add a saturated solution of pyrogallol in
chloroform: a brown coloration indicates the presence of molybdate.
In ~~ = kt
or, stated in other terms,
It = 10 . e - kt (3)
where lois the intensity of the incident light falling upon an absorbing
medium of thickness t, It is the intensity of the transmitted light,
and k is a constant called the absorption coefficient for the wave-length
and the absorbing medium used. By changing from natural to
Briggsian logarithms we obtain:
(4)
* Spectrophotometry proper is mainly concerned with the follGwing regions of the
spectrum: ultra-violet, 185-400 mIL (millimicrons); visible, 400-760 mIL; and infra-red,
0'76-15 fL (microns). In this chapter our attention will be confined to the visible
portion of the spectrum.
1 A = 01 ~fL = 10-4 fL = 1 X 10- 8 cm.
I mfL = 10 A = 10- 7 cm.
000 (Juantitative Inorganic Analysis
where K = k/2'3206 and is usually termed the extinction coefficient
(Bunsen and Roscoe, 1857). The extinction coefficient is generally
defined as the reciprocal of the thickness (t cm.) required to reduce
the light to -f-o- of its intensity. This follows from equation (4), since:
IdIo = 01 = lO-Kt or Kt = 1 and K = l/t
The ratio IdIo is the fraction of the incident light transmitted by a
thickness t of the medium, and is termed the transmission. Its
reciprocal Io/It is the opacity, and the optical density D of the
medium, sometimes designated the extinction E, is given by :
D = log Io/It
Thus a medium with optical density 1 for a given wavelength trans-
mits 10 per cent of the incident light at the wavelength in question.
Beer's law. We have thus far considered the light absorption and
the light transmission for monochromatic light as a function of the
thickness of the absorbing layer only. In quantitative analysis, how-
ever, we are mainly concerned with solutions. Beer (1852) studied
the effect of concentration of the coloured constituent in solution
upon the light transmission or absorption. He found the same relation
between transmission and concentration as Lambert had discovered
between transmission and thickness of the layer (equation (3)), i.e.,
the intensity of a beam of monochromatic light decreases exponentially
as the concentration of the absorbing substance increases arithmetically.
This may be written in the form:
It = 10 , e-k'c
or
(6')
This is the fundamental equation of colorimetry and sp~ctrophoto
metry, and is often spoken of as the Beer-Lambert law. The value of
E will clearly depend upon the method of expression of the concen-
tration. If c is expressed in gram mols per litre and t in centimetres
then E is the molecular extinction coefficient. The latter is equal to
the reciprocal value of the thickness in centimetres of a 1 molar solu-
tion (c = 1) at which: It = OlI o, since It = 10 .10 -K when t = 1 and
c = 1.
The specific extinction coefficient Es may be defined as the extinction
coefficient per unit concentration.
Where the molecular weight of a substance is not definitely known,
it is obviously not possible to write down the molecular extinction
coefficient, and in such cases it is usual to write the unit of concen-
tration as a superscript, and the unit of length as a subscript.
Thus E~~m. 325 mJL = 30
means that for the substance in question, at a wavelength of 325 mp"
a solution of length 1 em., and concentration 1 per cent (1 per cent
Colorimetric Analysis tiUl
by weight of solute or 1 g. of solid per 100 ml. of solution) log IolIt has
a value of 30.
We may recapitulate some of the various technical terms which are
in common use in colorimetric and spectrophotometric measurements:
The optical density D, also called the extinction E, of a medium is the
logarithmic ratio of the intensity of the incident light to that of the
emergent light, i.e.,
D = E = log (IoIIt) or It = 10 lO- n (7)
D is obviously related in a simple way to the molecular extinction
coefficient, since:
D = ECt
The molecular extinction coefficient is therefore the optical density
when the layer of solution is 1 cm. thick and the concentration of the
absorbing substance is 1 g .mol. per litre.
The transmission T is defined as the ratio of the intensity of the
transmitted to that of the incident light; thus:
T = It/Io
The term transmittance or transmittancy T e , widely used in the
U.S.A., is defined as the ratio of the transmission of a cell containing
the coloured solution to that of an identical cell containing water or a
blank solution.
The optical density D may therefore be put equal to the logarithm
of the reciprocal of the transmission :
D = log (lITr= -log T
The scales of spectrophotometers are often calibrated to read directly
in densities, and frequently also in percentage transmittance. It may
be mentioned that for colorimetric measurements 10 is usually under-
stood as the intensity of the light transmitted by the pure solvent,
or the intensity of the light entering the solution; It is the intensity
of the light emerging from the solution, or transmitted by the solution.
It will be noted that:
the extinction coefficient is the density for unit path length
K = D It or It = 10 . 10 - Kt
the specific extinction coefficient is the density per unit path length
and unit concentration
E. = Did or It = 1 0 lO- E ,et
the molecular extinction coefficient is the specific extinction coefficient
for a concentration of 1 g.-mol. per litre and a path length of 1 cm.
E = Dlct
Application of Beer's law. Let us consider the case of two solutions
)f a coloured substance with concentrations c1 and c2 These are
)laced in an instrument in which the thickness of the layers can be
tltered and measured easily, and which also allows a comparison of
602 Quantitative Inorganic Analysis
the transmitted light (e.g., a Duboscq colorimeter, Section V, 6).
When the two layers have the same colour intensity:
(8)
Here tl and t2 are the lengths of the columns of solutions with con-
centrations c l and C2 respectively when the system is optically balanced.
Hence under these c.onditions and when Beer's law holds:
(9)
A colorimeter can therefore be employed in a dual capacity: (a) to
investigate the validity of Beer's law by varying c l and C2 and noting
whether equation (9) applies, and (b) for the determination of an
unknown concentration C2 of a coloured solution by comparison with
a solution of known concentration Cl' It must be emphasised that
equation (9) is valid only if Beer's law is obeyed over the concen-
tration range employed and the instrument has no optical defects.
When a spectrophotometer is used it is unnecessary to make com-
parison with solutions of known concentration. With such an instru-
ment the intensity of the transmitted light or, better, the ratio Idlo
(the transmittance) is found directly at a known thickness t. By
varying t and c the validity of the Lambert-Beer law, equation (6),
can be tested and the value of may be evaluated. When the latter
is known, the concentration Cx of an unknown solution can be cal-
culated from the formula:
(10)
FIG. V, 4, 2.
and it is found that the colour of the unknown lies between 04 and
06 mg. per litre. The second series of standards may then be pre-
pared containing 040, 045, 0'50, 0'55, and 060 mg. per litre. Further
comparison may then show that the value lies between 045 and
050 mg. per litre, and for many purposes this should be returned as
048 mg. per litre. If a more accurate value is required, and provided
the colour intensity of the solution and also the
apparatus employed will permit of finer com-
parison, another series of standards covering thc
range of, say, 045, 0475, and 050 mg. per litre
may be made up and the unknown compared
with these standards.
For the comparison of colours in Nessler tubes,
the simplest apparatus consists of a modified test-
tube rack (Fig. V, 4, 2). It is constructed of
wood, finished dull black, and is provided with
an inclined opal glass reflector or mirror, arranged
to reflect light up through the tubes. The Nessler
tubes rest on a narrow edge, and do not come
into contact with the reflector. The unknown
and standards are compared by placing them
adjacent to each other and looking vertically
down through them.
There are a number of devices which employ
permanent coloured-glass standards; these are
usually prepared from Lovibond or similar
type glasses. An inexpensive model is shown in
Fig. V, 4, 3. This is the B.D.H. Lovibond nessleri-
FIG. V, 4, 3. meter * (for other similar apparatus, such as the
Lovibond comparator, see Section V, 9 on the
determination of pH). It consists essentially of a Bakelite case for
holding vertically two Nessler glasses between a reflector and a
detachable rotating disc having nine apertures containing a series of
graded, permanent glass colour standards. Each disc incorporates a
* The apparatus is manufactured by The Tintometer Ltd., Milford, Salisbury, in
association with British Drug Houses Ltd., Poole, Dorset.
Colorimetric Analysis 607
series of standards designed for one particular test conducted under
specified conditions. Discs are available for many of the common de-
terminations by colorimetric methods, and the manufacturers are con-
stantly extending the range. The discs at present marketed include:
ammonia (with Nessler's reagent); bismuth (with potassium iodide);
chlorine in water (with o-tolidine); cobalt (with nitroso-R-salt); copper
(with dithio-oxamide); iron (with thioglycollic acid); lead (with sodium
sulphide); manganese (with sodium bismuthate); nitrate (with phenol-
disulphonic acid and also with 2 : 4-xylen-l-ol); pH (various ranges
with different indicators); silicate (with ammonium molybdate); and
titanium (with hydrogen peroxide). A wider range of determinations
can be made with the discs supplied with the Lovibond comparator
(see Fig. V, 9, 2).
The B.D.H. Lovibond nesslerimeter can, of course, be employed
as a simple comparative colorimeter as described above; the colour
disc is then removed.
V, 5. Duplication method.-This method finds its chief application
in the so-called colorimetric titration. A known volume, say 50 or
100 mI., of the solution is placed in a Nessler cylinder (Fig. V, 4, 1)
and a measured volume of the reagent or reagents is then added.
An equal volume of water (50 or 100 mI.) together with the same
volume of the reagent is introduced into another similar Nessler
cylinder. For mixing the solutions both cylinders are provided either
with a glass tube on which a flattened bulb (ca. 1 cm. diameter) is
blown or with a stirring-rod of which the lower end is flattened to a
width of 1 cm. and over a length of several centimetres. The tubes
should also be provided with black- or brown-paper cylinders to
exclude light from' the sides. The colour intensities are compared by
holding the tubes close together over a white surface, such as a sheet
of opal glass or, better, in a Nessler tube-stand (Fig. V, 4, 2). A
solution containing a known concentration of the constituent being
determined is added to the blank solution from a burette (preferably
of the micro type) until the colours of the two solutions viewed by
looking down into the tubes match. As a rule, if the volume of the
standard solution required to match the colour of the unknown is
less than about 2 per cent of the total volume, the volume change
due to the addition of the reagent may be neglected. It may, however,
be allowed for by a simple calculation, or the determination may be
repeated by taking 100 - x (or 50 - x) mI. of water, where x is the
volume of the standard solution employed in the first titration. Several
determinations should be carried out, and the positions of the tubes
should be interchanged-thus that on the right-hand side should be
put to the left of the observer and vice versa.
It must be emphasised that this method can be applied only when
the colour is independent of the mode of mixing, for in one tube a
very dilute solution of the substance to be determined is mixed with
the reagent, whilst in the other tube a comparatively concentrated
solution of the substance is mixed with a dilute solution of the reagent.
The development of colour should be practically instantaneous and
remain permanent during the time required for the measurements;
foreign substances present in the unknown should not affect the colour.
The method is, at best, only an approximate one, but has the advantage
that only the simplest apparatus is required.
608 Quantitative Inorganic Analysis
V, 6. Balancing method. Plnnger-type colorimeters.-The plunger-
type of colorimeter with two halves of the field of view illuminated
by the light passing through the unknown and standard solutions
respectively was invented by J.
Duboscq of Paris in 1854. Various
ml. ml.
improved modifications of the instru-
ment were subsequently developed by
manufacturers of optical apparatus.
Before describing the latter, reference
must be made to Hehner cylinders (Fig.
V, 6, 1). These are utilised in pairs,
and are the simplest form of apparatus
employed in matching colours by the
balancing method. Each cylinder has
a glass stopcock about 25 cm. from
the bottom through which liquid may
be drawn off until the colour in the two
cylinders is the same in intensity when
viewed vertically. The cylinders are
FIG. V, 6, 1. graduated at 1-ml. intervals, and usually
have a capacity of 100 ml.; they should
have flat, carefully ground and polished bottoms of clear glass and be uni-
form in bore. It is advisable to place them in a box so arranged that the
light is reflected from the bottom of the latter up through the tubes.
A Dubosq colorimeter (the Watts "Microptic" colorimeter *) is
shown in Fig. V, 6, 2, and sectional diagrams in Figs. V, 6, 3 and V, 6, 4.
FIG. J', C, 2.
. COLOU R r--r--....
~'l1ATCHING 'I=~~
EYEPIECE
MILLED HEAD
CONTROLLING
CUPS
ILLUMINATING
LAMP
FIG. V, 6, 3. FIG. V, 6, 4.
is visible, light from one cup illuminating one half, and light from
the second cup illuminating the other half of the field. The depths
of the columns of liquids are adjusted by rotating the milled heads
on either side of the instrument, which raises and lowers the cups,
until the two halves of the field are identical in intensity, i.e., until
the dividing line practically disappears. When this condition holds
and Beer's law is applicable, the concentrations of the two solutions
are inversely proportional to their depths, which are normally read
on the scales on the side of the instrument.
In the "Microptic" colorimeter the two precisely divided glass
scales, reading directly to 01 mm. and so dispensing with the use of
x
610 Quantitative Inorganic Analysis
a vernier, are viewed simultaneously in the reading microscope (situated
immediately adjacent to the main eyepiece), which has a magnification
of X 10. The scales have a range of 60 cm.,
and readings can easily be made with the
aid of an index pointer to about one-fifth
of a division (002 mm.). The cups and
. plungers are all-glass, i.e., the bottoms
have ground and polished surfaces, and
are fused to the cylinders. Two sizes are
supplied with the instrument; the smaller
sizes have a capacity of ca. 1 m!. each, and
are employed with "micro" plungers
which are interchangeable with the larger
type. Each cup is provided with a
special fitting on the bottom, permitting
the insertion of either one or two Ilford
or Wratten filters. The front metal cover,
which forms a light shield and protection
FIG. V, 6, 5.
for the cups and plungers, slides on a
grooved fitting, and is easily removed for access to the CUp&.
Use of Duboscq-type colorimeter. The colorimeter must be kept
scrupulously clean. The cups and plungers are rinsed with distilled
water and either dried with soft lens-polishing material or rinsed with
the solution to be measured.
Make sure that the readings are zero when the plungers just touch
the bottoms of the cups. Place the standard solution in one cup,
and an equal volume of the unknown solution in the other; do not
fill the cups above the shoulder. Set the unknown solution at a scale
reading of 100 mm. and adjust the standard until the fields are
matched. Carry out at least six adjustments with the cup containing
the standard solution, and calculate the mean value.
The plungers should always remain below the surface of the liquid.
Since the eye may become fatigued and unable to detect small differ-
ences, it is recommended after making adjustment to close the eyes
for a moment or to look at something else, and then see if the adjust-
ment still appears satisfactory. It is advisable to approach the
match point both from above and from below.
If t1 and t z are the average readings for the cups containing the
solutions of known and unknown concentration respectively, and c1
and C z are the corresponding concentrations, then if Beer's law holds:
FIG. V, 7, 2.
.'
/
-8
1'6 x / '."_
Vl
- 1:'"'"
w
/ '100 $l.
~P- f---
w
1'2 / V
0
!-- !,! '" / ./
1:
/ /
0'8
o W
_j r?
V
./
......... - 5002-
1000' n
Isoon
, t-
......
"
100 200 300 0400 500
FOOT CANDLES
600
cPu.
f/~
q./
// .-
~SP
500
/J .... ::;;;--
Vl
w ~/ ./
.........
-0400- w
0..
'" /_'/ V
- 1: ./
0
300 u'" ~V
lOOO~ l -
l: ~/
2
100 ~
~ '/
--
~ V. . . .........
~ .........
- --
~~
~
Isooln_
I=--
FIG, V, 7,3,
100
//'
~
SPECTRAL REtpONSE
EEL CyLL
/ I;'
f: 80
)' ,~
~,
:>
i=
v;60
Z
/ .,
I:'
.'
I'
w
VI
w
>40
i=
//.,'
~El CELL WITH ./
. l' NO/r.,AL
EYE
\\ '~, \
CORRECTfON j'
...J
w FfLTER "''. [\
'" 20
,/ '~
o --- /
;,
,~~
~oo 500 600 700
WAVELENGTH (MILLIMICR.ONS)
614 Quantitative Inorganic Analysis
that of the human eye, particularly if a corrective filter is employed.
The spectral response of the "Eel" cell compared with that of the
eye is shown in Fig. V, 7, 4.
Light filters. Optical filters are used in colorimeters (absorptio-
meters) for isolating desired spectral regions. They consist of coloured
glass or gelatin impregnated with a dye, and possessing the property
of transmitting light from a specified region of the spectrum, the
other components being preferentially absorbed. Ilford spectrum
filters, Chance glass filters, or Corning glass colour filters are largely
used. The approximate peak of transmission of a series of Ilford
spectrum filters in combination with heat-absorbing filters (as used
with the Hilger Spekker absorptiometer-see below) are collected in
the following table; Fig, V, 7, 5 gives the transmission curves (ltS
0
5
I
i\
z
o
in
\
Vl 20
I:
Vl
z
~
I- IS i\
I\
w 607f
"z~
LJ 10
1\
~
a:
w 602 603
N" R
0..
i\
o
400 450
/\
500
\ YK;\ /
550 600
'\
FIG. V, 7.5.
-
100
z (
~ 80
I:
Z
~
60 -=
( I
~ ~ Jon
IX 0.R2
I-
'"
~4()
I-
Z
w
/'
I{GI~
~
+'~
20
O.BI
" LL '\_2
'~ ~
o
400 450 soo sso 600 650 700 75e
WAVELENGTH mIL
FIG. V, 7, 6.
* These two filters exhibit no drop in transmission above these values in the visible
spectrum.
A general idea of the filter to use may be obtained from the follow-
ing table due to Mellon (1945). It is the filter which gives the greatest
difference in reading between two concentrations of the unknown
solution.
616 Quantitative Inorganic Analysis
SUITABLE COLOUR FILTERS
COMPLEMENTARY COLOURS
INSTRUMENTS
* Manufactured by :
1 Evans Electroselenium Ltd., Harlow, Essex, England.
Hilger and Watts Ltd., Hilger Division. 98 St. Pancras Way, London, N.W.I.
3 Bausch and Lomb Optical Co., 642- W St. Paul St, Rochester 2, N.Y.
Unicam Instruments (Cambridge) Ltd., Arbury Works, Cambridge.
5 Fisher Scientific Company, 717 Forbes Street, Pittsburgh 19, Pa., U.S.A.
S Coleman Instruments Inc., 318 Madison Street, Maywood, Illinois, U.S.A.
Colorimetric Analysis 617
SOURCE
~
j\
I \
I \
/ "
I
~ COLLIMATING LENS
~
I :
i i FILTER
I I
, I
MOVABLE
HOLDER
,
I
~ , I
SOLUTION SOLVENT
BARRIERTYPE
-
PHOTO CELL
FIG. V, 7, 7.
FIG. V, 7, 8.
618 Quantitative Inorganic Analysis
controlled by a shutter. Eight Ilford filters (Nos. 607-S and 621-6)
are supplied. Matched test-tubes of 3 or 7 ml. capacity are employed.
LAMP . PHOTOCELL
SHUTTffiS (ADJUSTABLE)
REFLECTOR
FIG. V, 7, 9.
FIG. V, 7, 10.
"FLOATING SPOTLIGHT"
SAMPLE HOLDER
THUMB SCREW
, .
SAMPLE HOLDER
SWINGING COVER
PRECISION
CONTROL
FILTER HOLDER DIAPHRAGM
OPERATE
KNOB
($I
GAL>i}{HORT
SAMPLE HOLDER
(CUVETIE TYPE)
FIG. V, 7, lOA.
filter, a control diaphragm, a light (" interference ") filter, through the
sample (contained in a test-tube or cuvette), and finally strikes the
,barrier-layer cell. The current output of the barrier-layer cell is
I measured by a sensitive double-suspension galvanometer. The light
filters normally supplied (430, 500, 550 and 630 mfA-) have a narrow band
pass of ca. 20 mfA- and a transmission of about 40 per cent; filters for
other wave lengths are available.
620 Quantitative Inorganic Analysis
Unicam G.P. photo-electric colorimeter. This colorimeter
11) operates from a 6-volt battery or a constant-voltage
The light is controlled by a shutter mechanism operated by two
troIs, "coarse" and " fine." Ilford spectrum filters (No. 608
609 deep red, 621 violet, 622 blue, 623 blue green, 624 green,
yellow green, and 626 yellow) are supplied. The sensitive
meter is calibrated with a linear scale 0- 100 and a lO~~arll'inEnlC
the scale is removable, and can be substituted by
FIG . V, 7, 11.
FIG. V, 7, 12.
J FIG. V, 7, 13.
and enables the intensity of the light falling upon the photo-cell 0 to
be varied by known amounts. Since there is an image of the fila-
ments on the cell there is no change in the photo-cell area illuminated
when the aperture alters; only the quantity of light reaching the cell
is controlled by the variable aperture formed by the upper portion
of the circumference of the cam and the diaphragm limiting the area
of the light beam. The scale associated with the aperture is so cali-
brated that if R is the reading corresponding to a degree of opening
622 Quantitative Inorganic Analysis
such that the amount of light transmitted is l/A of that admitted
when the aperture is fully open, then R = log A. This function,
known as optical density, was chosen because it is approximately
linear with the concentration of a solution over small ranges. This
function is normally a logarithmic one, but by giving the cam disc J
a suitable contour, an evenly divided scale on the drum has been
provided; there is also a scale of percentage transmissions.
The cell at A simultaneously receives light from G of an intensity
controlled by an iris diaphragm E; the latter is uncalibrated, and is
used only for adjusting purposes and also as a fine adjustment for the
final setting. The two photo-cells A and 0 are connected in opposition
across a Cambridge spot galvanometer P, so that when the photo-
electric currents given by the cells are equal the galvanometer records
zero deflection. A variable resistance R is arranged to provide variable
sensitivity.
Use of Spekker photo-electric absorptiometer. This is best illustrated
by describing the procedure for making a determination. Let us
suppose that it is desired to compare the depth of colour or, more
precisely stated, the amount of light absorbed by two liquids 8 1 and S2'
the latter being the more deeply coloured, i.e., the more absorbing.
1. Place S2' contained in the special cell, into the beam, and open
the variable aperture to its full extent by setting the drum at zero.
2. Adjust the iris diaphragm in front of the compensation cell until
the galvanometer shows zero deflection.
3. Substitute S1 for S2' when the galvanometer will be seen to be
deflected.
4. Adjust the calibrated variable aperture by means of the drum until
the galvanometer returns to zero, and take the reading on the drum.
This series of operations takes less than half a minute. The cells
containing the liquids are mounted side by side, and are easily inter-
changed by pushing the slide along an inch or so until it clicks into
the correct position.
If we assume that the light intensity remains constant throughout
the series of operations, then the current given by the indicating cell
at the end of operation 4 is the same as at the end of operation 2
(since in each case it balances the output of the compensating cell).
The difference in the illumination condition in the two cases is that
in the second case the intensity-reduction produced by closing down
the aperture is substituted for the reduction produced by the absorp-
tion of the specimen. The ratio of the area of the partly closed aper-
ture to that of the aperture when fully open is thus a measure of the
absorption of the liquid. Since both photo-cells are affected alike by
changes in the intensity of the lamp, the reading is unaffected by
changes occurring during the series of operations.
The sensitivity of the instrument in detecting small differences
between the absorption of two liquids is greatly increased by the use
of an appropriate light filter; indeed, as indicated in Fig. V, 7, 13,
the use of a suitable light filter should be the normal practice (for a
discussion as to the choice of filter, see previous paragraphs on Light
Filters). A set of eight pairs of lIfOI'd spectrum filters, which have a
narrow band of transmission and a fairly sharp cut-off (see Fig. V, 7,5),
is normally supplied for use with the instrument. Sliding carriers are
provided for two filters which enable them to be interchanged quickly
Colorimetric Analysis 623
in the absorptiometer or changed at will. The all-glass cells for liquids
are available in lengths of 0'25, 05, 1, 2, and 4 cm.
It is a well-known fact that photo-electric cells under prolonged
illumination tend to behave irregularly. This difficulty is overcome
by the use of a gravity-controlled shutter which must be held open
while the readings are being taken. In this way the steady burning
of the lamp itself is ensured, and at the same time it is impossible to
expose the cells for any longer than is required for the reading to be
made.
For the routine use of the absorptiometer in colorimetric determina-
tions, it is necessary to prepare a calibration curve by taking readings
with a number of coloured solutions of known concentration covering
the required range. This calibration curve remains valid so long as
appreciable changes do not take place in the spectral sensitivity of
the photo-electric cells or in the colour of the filter. The changes in
the photo-cells and in the glass of the filters are generally very gradual,
and the calibration curve need be checked only at wide intervals,
say, every few months.
The advantages of the Spekker absorptiometer include:
(a) It runs directly from the electric mains supply; no batteries are
required.
(b) Owing to the use of the two balanced photo-cells, the readings are
independent of the fluctuations of the mains supply.
(e) The scale of the instrument is approximately linear with the con-
centration of the solution.
(d) The instrument readings are not affected by variations in the sensi-
tivity of the photo-cells or of the galvanometer, since a null method is
employed.
(e) The galvanometer, which indicates the photo-electric current, is a
robust but sensitive instrument of the spot type, and is used as a null
indicator.
(f) Readings can be taken with as little as 25 m!. of liquid with the
25-cm. cells; if a micro-cell is employed the volume can be reduced to
05 m!. The commonly used cell (1 cm.) has a capacity of approximately
8 m!.
Fisher electrophotometer. The instrument and a schematic diagram
of the optical arrangements and the electrical circuit are shown respec-
tively in Figs. V, 7, 14 and V, 7, 15. The light from the photometer
lamp, which is transmitted through a coloured solution, falls upon
one barrier-layer-type photo-cell, and the current generated is measured
in a potentiometer circuit by comparison with the current generated
by a second similar photo-cell illuminated directly from the same
source. The percentage light transmission of the solution is found by
comparison with the light transmission under identical conditions of
distilled water or the solvent, the transmission of which is taken as
100 per cent. The lamp is operated well below its normal rating,
and a switch is provided for varying the intensity of the light. The
lamp is controlled by a button which is left on only during the actual
readings. The cells (of circular or rectangular cross-section) have a
capacity of 23 or 3 mI., and a special dual-cell slide is provided which
permits rapid interchange of the positions of the unknown and of the
standard solution in the light beam. Three filters with the following
624 Quantitative Inorganic Analysis
characteristics are normally supplied: blue, 425 mfL (for red, pi
orange, and yellow solutions); green, 525 mfL (for yiolet and purp
solutions); and red, 650 mfL (for blue, violet, purple, and green sol
tions). The main scale on the instrument is a logarithmic one.
FIG. V, 7, 14.
FILTER
SAMPLE
FINAL INITIAL
<...~(-DJ_U_ST_"101-_ _N_U--l~..L,<
GALVANOMETER
FIG. V, 7, 15.
WAVELENGTH CONTROL
FIG. V, 7, 16.
n _-
-t- --
COLORIMETER LENS LENS SLIT SHUTTER CELL
_- ---
~--- ----
"
-----u
LAMP _
_lJ--
FIG. V, 7, 17.
PHOTOCELLS
AND
U NIT \ D
LIQUID
CELLS
CHECK
EASURIN G
ADJUSTMENT ADJU STMENT
NTROL /
ZERO-READ-CHECK
SWITCH
FlO . V, 7, 18.
MEASURING UNiT
IN '01 MMS .
P. E. CELL BOX
COLORIMETER UNIT
FIG. V , 7, 20.
FIG. V, 7, 21.
FIG. V, 7,22.
654
I~
\ GALVANOM ETER GALVANOMETER
\ INDEX SCALE UOFF
\
\
\ MIRROR
\ /\
/ \
\ / \ ,
GALVANOMETER
LAMP
\/, rp
GALVANOMETER
\ ~
I LENS
INDEX
MIRROR ,
J
..-------~"""-'
I GALVANOMETER
WAVELENGTH
CAM
_a_
C::7LENS
~
. ' ''~WOOD ' S
eCHELETTE
II, ,;ILENS GRATING
11'1/'
, ~} }.,/ SPECTRUM
~)\CJ MONOCHROMATOR
~ EXIT SLIT
~LHIS<S
FILTER
L._-C_==,'I-. PHOTOCRL
FIG. V, 7, 23.
THUMB
SCREWS
FIG. V, 7, 25.
AMPLIFIER
FIG. V, 7, 26.
A dispersed image is then formed in the plane of the exit slit G. After
passing through a focusing lens H , the light passes through the sample
cell I (housed in the sample compartment) to the photo-cell K; J is
a shutter control for the light falling on the photo-cell. The output
Colorimetric Analysis 633
of the photo-cell K is amplified by a multiple-stage electronic circuit
for the operation of the meter, which directly indicates per cent trans-
mittancy (To) and absorbance or optical density (- log T,) of the
sample being analysed.
Beckman model DU quartz spectrophotometer. This is a precision instru-
ment. Two interchangeable light sources are used; a 6-volt, 25-
watt tungsten-filament lamp, operated from a storage battery, for
measurements down to 320 mfL; a hydrogen-discharge lamp, operated
from the 110-volt, 50/60-cycle mains with electronic voltage control,
for measurements in the ultra-violet region below 320 mfL. It employs
a quartz prism of the Littrow type with a concave mirror of 50 cm.
focal length for collimation; the relative aperture of the system .is
about F /11. The slit mechanism is continuously adjustable to 001 mm.
The band-spread of the monochromator can, if necessary, be adjusted
to less than 1 mfL with the appropriate setting of the slit opening over
most of the spectral range of the instrument. The wavelength scale
is calibrated 200-2000 mfL, but the practical limit with present light
sources is 200-1000 mfL . . Two photo-cells are employed: a red-
FIG. V, 7, 27.
sensitive photo-tube for use above 625 mfL (but usable to 400 mfL),
and a blue-ultra-violet-sensitive photo-cell for work at 200-625 mfL.
The photo-tube current is measured by a null method utilising a slide-
wire potentiometer and an electronic amplifier. The potentiometer is
calibrated in per cent transmission from 0 to 110 and in optical
densities from 0 to 20; a switch is provided which increases the
sensitivity by a factor of 10, thus giving greater accuracy in reading
transmission values below 10 per cent and at the same time extending
the optical density range from 10 to 30. Controls are provided inter
alia for adjusting the dark current to zero and the percentage trans-
mission to 100. Four standard 10-mm. light-path absorption cells of
Corex are supplied in a four-place cell-holder; an interchangeable cell
compartment is available to accommodate either Corex or fused-
silica cells of 10-, 20-, 50-, and 100-mm. light paths as well as test-
tubes of 10-25 mm. diameter.
Schematic diagrams of the optical system and of the electronic
wiring systems are given in Figs. V, 7, 27 and V, 7, 28 respectively,
and the instrument is shown in Fig. V, 7, 29. An image of the light
source A is focused by the condensing mirror B and the diagonal
mirror 0 on the entrance slit at D. The entrance slit is the lower of
two slits vertically over each other. Light falling on the collimating
mirror E is rendered parallel, and is reflected towards the quartz
L. ,
634 Quantitative Inorganic Analysis
prism F. The back surface of the prism is aluminised, so that light
refracted at the first surface is reflected back through the prism,
undergoing further refraction as it emerges from the prism. The
collimating mirror focuses the spectrum in the plane of the slits D,
and light of the wavelength for which t)'le prism is set passes out of
...__--+o+~
DARK
CURRENT
I
O--+-----1-+----?-+-f- P"--+-+---- K : ; + 21
STORAGE I V.,
BATTERY I 1
I
I
I I
.----"""7L::::."<J -_J
-1-
FIG. V , 7, 28.
FIG. V, 7, 29.
the monochromator through the exit (upper) slit, through the absorp-
t ion cell G to the photo-cell Ii.
I t may be mentioned that accessories are available for the measure-
ment of fluorescence, diffuse reflectance, and flame spectrophoto-
metry, and also for temperature control of the sample compartment.
V, 8. Turbidimetry, nephelometry and fluorimetry.- A coloured
substance in true solution may be determined by comparison with a
standard-this is one aspect of the true colorimetric method. The
transmission of light is measured, and its reflection is zero. With a
Colorimetric Analysis 635
colloidal dispersion of a coloured precipitate, however, transmission
and also some reflection of coloured light occurs. If it can be assumed
that the reflection is negligible, then the ordinary colorimetric methods
of determination may be applied; here We have the phenomenon
of turbidimetry, and the instrument is used as a turbidimeter. If the
reflection is appreciable, colonmetric methods are subject to serious
errors; in such cases the reflection (and the accompanying diffeaction)
of the light is measured at right angles to a parallel beam of incident
light (the so-called Tyndall light). The
process of measurement is then called
nephelometry, and the instrument is termed
a nephelometer. A nephelometer therefore (A)
tI II II rI
LIGHT BEAM
compares scattered light and not trans-
mitted light: it measures turbidities by
~ JIJ1= p~~~C'"
M"w~e~
comparison with a standard. When some
substances in solution are irradiated by
ultra-violet light, fluorescence is produced,
i.e., radiation is emitted which has wave- SOLUTION
lengths characteristic of the light-absorb-
ing molecules and not only that of the
incident beam. The fluorescence is usually til
I I 1
t
LIGHT BEAM
o bserved and measured in a direction at
right angles to a parallel beam of incident (B) I , I I PHOTO
light; the process of measurement is then , _ _ _ _ _]CELL
termed fluorimetry and the instrument a ----
fluorimeter. * The techniques of nephelo- ----
metry and fluorimetry are therefore very ----
similar in practice, although quite different SUSPENSION
in theory. Nephelometry is based upon
the scattering of light, without change of
wavelength, of colloidal suspensions, and t t
II
1 I I I LIGHT BEAM
makes use of a physical phenomenon largely
independent of the chemical nature of the (C) III PHOTO
o--~-~~~'
dispersed particles. Fluorimetry depends
upon the chemical properties of particular
molecules, and can be used to detect and
to measure quantitatively specific solutes
in filtered homogeneous solutions; the SOLUTION
FIG. V, 8, 2. '
F IG . V, 8, 3.
FIG. V, 9, 2.
aperture through which the solution in the cell (or cells) can be observed.
As the disc revolves, the value of the colour standard visible in the
aperture appears in a special recess. The Lovibond comparator * is
shown in Fig. V, 9, 2; this may be used with 135-mm. test-tubes or
* Manufactured by The Tintometer Ltd., Milford, Salisbury, England. The" all-
purpose" comparator is similar, but has wider applications .
.,
640 Quantitative Inorganic Analysis
135-mm. rectangular cells. A similar apparatus is marketed by
Hellige, Inc.* (Fig. V, 9, 3, a), but this comparator includes a prism
attachment by means of which the two colours being compared are
brought side by side in the eyepiece (Fig. V, 9, 3, b). A particularly
( b)
FIG. V, 9, 3.
The arsenic must be in the tervalent state. Nitric acid, the halogens,
and compounds that yield sulphur dioxide, hydrogen sulphide, or phosphine
must be absent. The last-named are readily eliminated by boiling with
nitric acid; the excess of the latter is removed by evaporation with sulphuric
acid to fumes of sulphur trioxide. In such treatment the arsenic becomes
quinquevalent and must be reduced, e.IJ., with ferrous sulphate, hydrazine
sulphate, or by heating with potassium iodide and stannous chloride solu-
tion. The following metals and their salts are undesirable: silver, mer-
cury, platinum, palladium, nickel, cobalt, and copper. In the presence of
interfering substances, it is usually best to separate the arsenic first as the
trichloride by distillation in an all-glass apparatus from a solution con-
taining hydrochloric acid and a reducing agent, such as hydrazine sulphate.
/
o
HgCI2
paper
FIG. V, 22, 1.
about 2 mm., is passed through the other hole: a hole of about 2 mm.
diameter is made in C (below the cork) to allow of the free escape of
the gases. The upper end of C is ground smooth (e.g., on a fine
carborundum stone) at right angles to the tube, and is fitted with a
device whereby the mercuric chloride paper is held firmly in position
over the opening of the tube, thus ensuring that all the arsine evolved
passes through the paper and a uniform circular stain is IJroduced.
The simplest of thef:;e is to fit a wide tube (about i in. long and ca.
1 in. internal diam()ter) round the upper part of C by means of a
cork and also to provide another cork, bored with a hole equal in
diameter to the external bore of the tube, which fits tightly on to the
fiat end of C. A circle of mercuric chloride paper (about 10 mm. in
diameter) is cut out by means of a cork borer and placed on top of
the tube; the papee is held firmly in position by inserting the other
bored cork (see Fig. V, 22, 1 b). A. J. Lindsey (1930) has developed
an all-glass apparatus * (Fig. V, 22, 1, c) which serves the same pur-
pose; the tube is 20 cm. long, with internal bore 5 mm. or 65 mm.,
and is provided with a flange and two ears at the upper end. The
* Supplied by Baird aud Tatlock (London) Ltd., Freshwater Road, Chadwell Heath,
Essex, England. ,
658 Quantitative Inorganic Analysis
paper is placed on this flange and is held securely in position by means
of a cap with an identical flange, the upper part of which is worked
into a double-lipped shape; the cap and tube are held together by
means of a pair of rubber bands.
Roll one of the prepared lead acetate papers in the form of a cylinder
10 cm. in length and place it so that the upper end is not less than
25 cm. below the upper end of the tube; alternatively, the tube
may be packed with strips of the lead acetate paper about 10 cm.
in length.
Prepare a series of standard stains, covering a range of, say, 0001-
005 mg. of As, as follows. Place 5-10 g. of arsenic-free zinc (e.g.,
A.R.) in the bottle, together with about 05 g. of A.R. stannous
chloride. Fit the apparatus together, and place one of the prepared
discs of mercuric chloride paper into position as described above.
Introduce 2 ml. of the arsenic solution (0001 mg. per ml.) into the
flask, and then run in 50-55 ml. of 25N-sulphuric or hydrochloric acid
(prepared from the A.R. acids), and close the tap. Immerse the
bottle in a large beaker of water containing water at room tempera-
ture. Allow the reaction to proceed for 1 hour, then remove the
mercuric chloride paper disc and dry it in the dark on a sheet of
filter-paper. Repeat the procedure with fresh discs, using increasing
amounts of arsenic solution. Mark each disc clearly with the exact
arsenic content.
If the standards are likely to be used frequently, a fair degree of
permanence may be secured by any of the following procedures:
(i) dry the discs between filter-paper, and (a) dip them into cellulose
varnish, mount on a sheet of white paper, and preserve over calcium
chloride in a desiccator in the dark or (b) dip the discs into molten
paraffin wax, and preserve them over phosphoric oxide in a closed
tube which is kept in the dark; (ii) immerse the discs in a 10 per cent
solution of potassium iodide until the red colour of mercuric iodide
at first produced disappears, leaving a brown stain, and then dry in
the dark on a sheet of filter-paper. Prepared papers, which are claimed
to preserve their permanence for 1 year, are available commercially.
If the arsenic content of the solution is approximately known,
the solution is added to zinc and stannous chloride contained in the
bottle, dilute sulphuric or hydrochloric acid introduced, and the
determination carried out exactly as in the preparation of the standards.
If the arsenic content is entirely unknown and interfering substances
are absent, a preliminary test should be carried out as follows. Set
up the apparatus, add the acid to the zinc, and then run in the arsenic
solution in suitable quantities at a time, commencing with 1 ml. and
waiting 15 minutes after each addition until a stain is produced within
the range of standards. The procedure is then repeated in the manner
used in preparing the standards, taking the appropriate amount of
the arsenic solution. The reagents should first be tested for the
presence of arsenic by running a blank with distilled water.
B. Electrolytic (mercury cathode) method. A mercury-cathode cell, due
to T. Callan and Jones (1930), suitable for the determination of small
quantities of arsenic, is sho-w11 in Fig. V, 22, 2, a.
It consists of a flat-bottomed tube, 5 in. long and Ii in. in diameter,
having an aperture of 1 in. diameter blown on the side about! in. from
Colorimetric Analysis 659
the bottom of the tube. The aperture is covered by a piece of parchmentised
paper,* which acts as an efficient diaphragm of very low electrical resist-
ance between the catholyte and anolyte. The aperture is flanged so that
the parchment paper may be held in position by means of a rubber band.
Purified mercury is placed in the bottom of the tube so that its surface is
just below the level of the aperture. Electrical connexion is made with
the mercury by means of a narrow glass tube, into the lower closed end of
which is sealed a short platinum wire. The whole of the exposed platinum
wire dips into the mercury; a little mercury is placed inside the tube, and
a copper wire dipping into this forms the negative terminal of the cell.
The narrow tube, carrying the cathode lead, passes through a three-holed
rubber stopper which closes the cell. The rubber stopper also carries a
tap funnel of 20 ml. capacity, through which the electrolyte or test solution
+
GROUND
GLASS
JOINT
(a) (b)
FIG. V, 22, 2.
may be introduced, and also an exit tube having a small hole near the
bottom and which is connected directly with the purifying tube of the
Gutzeit apparatus (not shown). The cathode cell is immersed in thlil
electrolyte of the anode cell (1 : 8 sulphuric acid), which is itself immersed
in a cooling-bath maintained at room temperature. The anode is a sheet
of platinum foil (2 in. by 1 in.) welded to a short length of thick platinum
wire.
Fig. V, 22, 2, b shows the essential parts of the same apparatus, but with
the rubber stopper replaced by a ground-glass joint.t
/.,
ing 16 g. of A.R. stannous chloride in 20 mI.
of water containing 1 mI. of A.R. hydrochloric
acid (sp. gr. 12).
The apparatus used is shown in Fig. V, 22,
3. It consists ofa 60-mI., wide-mouthed bottle
in the mouth of which is fitted by means of a
rubber stopper a tube 12 em. long and 125 em.
in diameter and constricted 5 cm. from the top.
The lower part of the tube contains a roll or
strips of heavy filter-paper soaked in 10 per cent
lead acetate solution and dried (this filter-paper
is held in position by a plug of purified glass
wool, which also serves to remove acid spray);
the upper portion contains purified glass wool
soaked in the same solution. This tube is con-
nected by a rubber stoppel' to a glass tube 10 em.
long and 4 mm. internal diameter which is con-
stricted 4 cm. from the lower end; the strip of
test paper is placed in this tube. In order to
obtain uniform results which are independent of
the temperature of the laboratory, a small
water-condenser, through which water below
20 C. is circulated, surrounds the tube con-
taining the test-strip.
Place the solution under test (containing
not more than 002 mg. of AS 2 0 3 ) in the gen-
erating bottle, add sufficient acid so that the
SOLUTION acid content is equivalent to 42-63 g. of
sulphuric acid, then introduce 2 mI. of the
ZINC ferric solution t and 05 mI. of the stannous
chloride solution: dilute to 50 mI. Introduce
FIG. V, 22, 3. about 15 g. of arsenic-free zinc (preferably in
the form of shot, i-i-in. mesh). Immediately
insert the connecting tubes, and place the mercuric bromide strip (120 X
25 mm.) in position; shake the bottle gently and allow to stand for
60 minutes. The temperature should be maintained at 20 10 C.
(or, less satisfactorily, at 25 1C.) by immersing the bottle in a
water-bath or a large beaker containing water at this temperature.
Remove the strip, dry it between sheets of filter-paper, dip it into
either cellulose varnish or into molten paraffin wax (free from water),
* Formerly more concentrated solutions (up to 5 per cent) of mercuric bromide
were employed. The weaker the solution, the longer and the less intense will be the
stain.
t Ferrous iron prevents polarisation between the zinc and acid, and hence accelerates
the liberation of the arsine.
Colorimetric Analysis 661
and mount it on a sheet of white paper. Compare the stain produced
with stains obtained in the same manner by known amounts of arsenic,
using portions of a standard solution containing 0001, 0'002, 0004,
0006, 001, 0015, and 002 mg. of As 20 3 and adding water, acid, etc.,
so as to have the same volume and concentration as the final unknown
solution. The strips bearing the standard stains should be mounted
on a sheet of white paper, folded back to form a cylinder and pre-
served in the dark in a closed test-tube containing phosphoric oxide.
A blank determination must, of course, be carried out with the reagents;
this should show n,t more than 0001 mg. of As 20 3 Instead of direct
comparison with standards, the lengths of the stains by a given pro-
cedure may be plotted on a graph and values interpolated; results
accurate to 5 per cent are obtained.
Procedure (molybdenum-blue method). The arsenic must be in the
trivalent state; this may be secured by first distilling in an all-glass
apparatus with concentrated hydrochloric acid
and hydrazine sulphate, preferably in a stream of
carbon dioxide or nitrogen. Another method c
consists in reducing the arsenate (obtained by
the wet oxidation of a sample) with potassium
iodide and stannous chloride: the acid con-
centration of the solution diluted to 100 ml.
must be diluted below 5 per cent; 1 ml. of 50
per cent potassium iodide solution and 1 ml. of o
a 40 per cent solution of stannous chloride in
concentrated hydrochloric acid are added, and
the mixture heated to boiling.
Transfer an aliquot portion of the arsenate
solution, containing not more than 01 mg. of A
E 25' -- EO -
00591
-n-- p e
M n+
( 1')
pH = 4'000 + tC ~~5r
The pH at 25 C. of the following solutions are known with an accuracy of
at least 001, and have been determined in accordance with the above
definition: 0lM-KHC204,H2C204,2H20, 148; O'OlM-HCl + 0'09M-KCl,
2'07; 0'lM-CH 3 'COOH +0'lM-CH 3 'COONa (prepared from pure acetic
acid, diluted, and half.neutralised), 4'64; 0025M.KH 2P0 4 0025M. +
Na 2HP0 4 ,12H 20, 685; 005M.Na 2B 4 0 7 ,lOH 20, 918. These solutions may
* At any other temperature T, the expression becomes:
E = -00001982T.pH
where T is the absolute temperature.
t pH Scale (British Standard 1647: 1950). For a comprehensive review see R. G.
Bates, "Definitions of pH Scales" (Chemical Review8, 1948,42, 1).
Potentiometric Titration Methods 675
be employed for the calibration of the glass electrode when an accuracy of
O'OI pH unit is desired. If an accuracy of 0'03 pH is acceptable, a wide
choice of solutions is available (see Appendix; Section A, 10).
VI, 2. Determination Of\H.-A. The hydrogen electrode. A typical
hydrogen electrode has already been described (Section I, 43). For
routine work, the most convenient source of hydrogen is the compressed
gas, sold in cylinders; a steady stream of hydrogen gas may be readily
obtained bv means of a reducing
~ ~~~~~w
va1ve. The gas may be passed.
through all-glass wash bottles contain- t
ing respectively 02N-potassium per-
manganate solution, alkaline pyro-
gallol solution (1-2 g. of pyrogallol in
ca. 35 ml. of 4N-sodium hydroxide
solution), dilute sulphuric acid (ca.
OIN; to neutralise alkali which might
splash over), and distilled water, be-
fore reaching the electrode. If a
hydrogen electrode is immersed in a [H+I=l rv!- _:}~~[~ ~-
solution the pH of which is to be de- FIG. VI, 2, 1.
t~rmined, and the half-cell is coupled
with a normal hydrogen electrode by means of a saturated potassium
chloride bridge (Fig. VI, 2, 1) in order to eliminate the liquid-junction
potential, * the e.m.f. of the resulting cell :
Pt I H 2 , H+ II H 2 , H+ I Pt
a=I a=x
may be measured by means of a potentiometer (see below). The e.m.f.
of this concentration cell at 25 C. (see Section I, 44) is given by :
_ 0.0591 c"
E - - - - 1og-,
n c1
00591 1
-1- log [H+]'
= 00591 pH;
or pH = E /0'0591.
The following notes on the preparation and the use of the hydrogen
electrode may be useful. The hydrogen ions of the solution are brought
into equilibrium with the gaseous hydrogen by means of platinum
black; the latter adsorbs the hydrogen and acts catalytically. The
platinum black may be supported on platinum foil of about 1 sq. cm.
total area: a platinum wire, 1 cm. long and 03 mm. diameter, is often
satisfactory. The platinum electrode is first carefully cleaned with
hot chromic acid mixture and thoroughly washed with distilled water.
* The open ends of the bridge are plugged tightly with pure filter-paper or fitted with
sintered-glass plates in order to minimise diffusion effects. In practice, it is usually
more convenient to employ a gel formed from 3 per cent agar in saturated potassium
chloride solution, the so-called agar-potassium chloride bridge. This gel is prepared
by heating 3 g. of agar, 30 g. of A.R. potassium chloride, and 100 ml. of water gently
until all has dissolved and the solution is clear. The narrow, U-shaped tubes are filled
by suction with the warm solution: upon cooling, the solution sets to a gel. The
siphons can be kept for prolonged periods if their open ends are placed, when not in
use, in a saturated solution of potassium chloride.
676 Quantitative Inorganic Analysis
Then it is plated from a solution containing 30 g. of chloroplatinic
acid and 25 mg. of lead acetate per 100 ml. with platinum foil aE
an anode. The current may be obtained from two accumulatorE
connected to a suitable sliding resistance; the current is adjusted to
produce a moderate evolution of hydrogen, and the process is complete
in about 2 minutes. It is important that only a thin, jet-black deposit
be made; thick deposits lead to unsatisfactory hydrogen electrodes.
After platinising, the electrode must be freed from traces of chlorine:
it is washed thoroughly with water, electrolysed in ca. 05N-sulphuric
acid as cathode for about 30 minutes, and again well washed with water.
Hydrogen electrodes should be stored in distilled water; they should
never be touched with the fingers. It is advisable to have two hydro-
gen electrodes so that the readings obtained -with one can be periodically
checked against the other.
The electrode depicted in Fig. VI,2, I is the Hildebrand bell-type. ThE
platinum electrode proper is surrounded by an outer tube or bell into
, ~ which hydrogen enters through a side
inlet, escaping at the bottom through
the test solution. There are four
small holes near the bottom of the
bell; when the speed of the gas is
suitably adjusted, the hydrogen
escapes at the bottom only, whilst
the test solution running through the
side holes gives the former an oscilla-
tory motion-a process which pro-
motes rapid saturation of the
electrode. The Lindsey hydrogen elec-
trode, illustrated in Fig. VI, 2, 2 has
many valuable features and utilises
5-7 ml. of the test solution. The
introduction and the removal of the
test solution is simple, and rapid
FIG. VI, 2, 2. saturation of the platinum is readily
attained. The hydrogen-outlet trap
is at right angles to the plane of the paper; and not in the same
plane as indicated in the figure. The funnel limb serves for filling and
washing out the vessel, and also supplies the connexion to the reference
electrode. The hydrogen stream is adjusted to produce a pulsating
movement up and down the platinum electrode.
The use of the normal (or molar or standard) hydrogen electrode as
a standard electrode or half-cell presents certain practical difficulties.
It is usual to employ a reference electrode as a secondary standard half-
cell; the potential of the reference electrode relative to the normal
hydrogen electrode is known with accuracy. The most widely used
reference electrode, due to its ease of preparation and constancy of
potential, is the calomel electrode. A calomel half-cell is one in which
mercury and calomel are covered with potassium chloride solution of
definite concentration; this may be OIN, l'ON, 35N, or saturated.
The potassium chloride solution must be saturated with the calomel.
The potential of, say, the saturated calomel electrode (i.e., that pre-
pared with saturated potassium chloride solution) must first be deter-
mined with reference to the normal hydrogen electrode. Let this value
Potentiometric Titration Methods 677
be designated Eca!. sa!'. :ij'or the measurement of the hydrogen-ion
concentration, we then enJploy the cell :
Hg [ H82C12' KCI(satd.) II H+, H21 Pt
Let the resultant e.m.f. be E obs . Then, at 25 C. :
E obs = Eca!. sa!. - 00591 log [H+]
pH = E obs . - Eoa!. sat.
00591
The potentials of the OIN, ION, and saturated calomel electrodes
at 25 C. relative to the normal hydrogen electrode are 03371, 02846,
and 02458 volt respectively.
Various forms of the calomel electrode are illustrated in Fig. VI, 2, 3;
OIN, N, or saturated potassium chloride may be used, but the last-
named is generally preferred for routine work. One of these, (a), will
~ ..
c
Potassium
chloride
solution
FIG. VI, 2, 5.
RHEOSTAT
a o - 0 0+
GALV + + STD. CELL
FIG. VI, 2, 6.
Potentiometric Titration Methods 681
the cell under measurement that it may be connected directly to the
two electrocJs. .
The hydro~en electrode cannot be used in solutions containing oxidis-
ing agents, e.g., permanganate, nitrate, ceric and ferric ions, or of
other substances capable of reduction, such as unsaturated organic
compounds, or in the presence of sulphides, compounds of arsenic, etc.
(catalytic poisons) which destroy the catalytic property of platinum
black. It is also unsatisfactory in the presence of salts of the noble
metals, e.g., copper, silver, and gold, and also in solutions containing
lead, cadmium, and thallous salts. There are many other electrodes
which are more convenient to use in the range in which they are applic-
able. Some of these will be described below.
Mention must, however, be made of the advantages of the hydrogen
electrode: (I) it is a fundamental electrode to which all measurements
of pH are ultimately referred: (2) it can be applied over the entire
pH range; and (3) it exhibits no salt error.
B. The quinhydrone electrode. The preparation of reproducible hydro-
gen electrodes is a comparatively tedious process and, moreover, the
electrode has certain limitations (see previous paragraph). E. Biil-
mann (1921) has introduced the quinhydrone electrode: this renders the
determination of pH a rapid and silllple process, and does not require
the use of hydrogen gas. Quinhydrone is a compound of quinone and
hydro quinone , and in solution is decomposed into equimolecular
quantities of these substances:
C6H402C6H4(OH)2 = C6H 40 2 + C6 H 4(OH)2
quinhydrone quinone hydroquinone_
H,Q
RT I aQ RT I
= E o
+ 2F oge -
aH,Q
+ -F ogeaH+
where a Q, aH +, and aH,Q are the activities of the quinone, hydrogen ions,
and hydro quinone respectively, and Eo is the standard potential
referred to the molar hydrogen electrode. Now under those conditions,
in which quinhydrone dissociates to give equimolecular quantities of
quinone and hydro quinone, the ratio of the activities may be regarded
as constant, hence:
(I)
FIG. VI, 2, 9.
R,
FIG. VI, 2, 10.
the electrical circuit in Fig. VI, 2, 10, and the dip-type of calomel
electrode in Fig. VI, 2, 11; the glass electrode calls for no further
comment. This instrument is designed mainly for use with the glass
electrode, and is calibrated directly for the pH range 0- 14 in 002 units.
* For example by :
Cambridge Instrument Co., Ltd., 13 Grosvenor Place, London, S.W.I.
Muirhead and Co., Ltd., EImers End, Beckenham, Kent.
Electronic Instruments, Ltd., Richmond, Surrey.
General Electric Co., Ltd., Kingsway, London, W.C.2.
Pye and Co. Ltd. , Newmarket Road, Cambridge.
National Technica l Laboratories, 820 Mission Street, South Pasadena, California,
U.S.A. (manufacturers of Beckman pH meters).
Potentiometric Titration Methods 687
The galvanometer acts as a null-point det~ctor; compensation is
provided inter alia for the temperature of the test solution. In some
forms of the instrument a standard ~
cell is incorporated, and can be
hrought into circuit for standardis- T
ing purposes at any time. The
instrument may be used, by throw-
ing a switch, also as a millivolt
potentiometer; each division repre-
sents 2 millivolts, and the total
range is 0- 1400 millivolts.
The Cambridge direct-reading pH in-
dicator . (Fig. VI, 2,12) is a robust C1
CAL O MEL ELEMENT
instrument, also designed for use KCI . SOLUTION - :
with t4e glass electrode, covering the ~. - C
range 0- 14 pH, and directly readable - 2
to 01 and by estimation to 005 pH.
Standardisation against a standard
buffer solution is carried out daily; MERCURY
temperature compensation for the
solution in the electrode system is CALOMEL & KCI
provided for by a dial in the front of
COTTON WOOL ,
the apparatus. PLUG KCI. CRYSTALS
The Beckman pH meter (model G)
is presented in Fig. VI, 2, 13. The
dial covers the pH range 0- 13, and
is graduated in 01 pH units; read-
ings may be made by estimation to R
002 pH unit. A temperature-com- FIG. VI, 2, 11.
pensation device is incorporated. A
switch enables the instrument to be used for millivolt readings on
the meter scale, the scale then becomes 0- 1300 millivolts instead of
0'05M-sodium borate (pH 918 at 20) are frequently used (see Section
VI, I). The standard acetate buffer, i.e., an aqueous solution which is
O'lM with respect to acetic acid and also sodium acetate, has a pH
of 464 at 20 and is an excellent standard; it is prepared by mixing
200 ml. of M-acetic acid with 100 ml. of M-sodium hydroxide and
diluting to 1 litre with distilled water.
VI, 3. Potentiometric titrations.- Classical method. In the previous
section the determination of the hydrogen-ion concentration of a
solution was described; this involved the measurement of the e.m.f.
between two electrodes, one an indicator electrode, the potential of
which was a function of the pH of the solution, and the other a refer-
ence electrode of constant potential. In potentiometric titrations
absolute potentials or potentials with respect to a standard half-cell are
not usually required, and measurements are made whilst the titration
is in progress. The equivalence point of the reaction will be revealed
by a sudden change in potential in the plot of e.m.f. readings against the
volume of the titrating solution; any method which will detect this
abrupt change of potential may be used. One electrode must maintain
a constant, but not necessarily known, potential; the other electrode
must serve as an indicator of the changes in ion concentration, and
Potentiometric Titration Methods
must respond rapidly. The solution must, of course, be stirred during
the titration. A simple arrangement for potentiometric titration is
given in Fig. VI, 3, 1. A is a reference electrode (e.g., a calomel half-
cell), B is the indicator electrode, and G is a mechanical stirrer; the
t
~
'-'..JL_----
<i
~ Volume. mi.
FIG. VI, 3. 1. Fro. VI, 3,2.
FIG. VI, 3, 3.
690 Quantitative Inorganic Analysis
solution to be titrated is contained in the beaker. The e.m.f. of the
cell incorporating the initial solution is determined, and the measure-
ment is repeated at intervals of 1 ml. addition from the burette. When
the em.f. changes somewhat more rapidly as the end point is approached,
the e.m.f. readings are taken at more frequent intervals, and eventually
after each drop. After the first rough titration, the exact procedure
will be apparent. Draw a curve with the e.m.f. readings as ordinates
and the burette readings as abscissffi; the point of inflexion (or the
middle of the steepest portion of the curve) is regarded as the end point
of the titration. A more satisfactory determination of the end point
is obtained by the differential method, in which the change of e.m.f.
per unit volume of titrant is the ordinate. If we plot the change of
potential in millivolts caused by Ol-ml. increments of the reagent
(6.E /6. V) against the middle of the titration interval, a curve of the
type shown in Fig. VI, 3, 2 is obtained. The abscissa corresponding
to the maximum gives the end point of the reaction with sufficient
accuracy for all ordinary purposes.
A commercial form of the simple potentiometric-titration apparatus
is available from the Cambridge Instrument Company, and is illustrated
in Fig. VI, 3, 3. The apparatus comprises an electrode system (plati-
num; eaJomel elect.rode; 3nt.jmony eleciJ'ode, et.c.) with a st.irring
motor, a potentiometer, and a robust, sensitive" spot" galvanometer
of high resistance. A coarse and a fine adjustment and also a sensitivity
control are provided on the high-resistance galvanometer. In use the
electrodes are connected to two terminals at the rear of the galvanometer.
The approach of the end point of the titration is indicated by temporary
deflections of the galvanometer" spot" of increasing magnitude, and
the end point is shown by a sudden large and permanent deflection; the
sensitivity control renders it easy to avoid over-running the end point.
It is possible by means of the differential method of potentiometric
titration to obtain values of 6.E /6. V directly, and thus to increase con-
siderably the accuracy of the determination of the end
point. The procedure depends upon the concentration
polarisation of one of two similar electrodes by some
mechanical device which prevents mixing of a small
portion of liquid surrounding One electrode with the re-
mainder of the solution being titrated. A simple device
for this purpose is depicted in Fig. VI, 3, 4. A small
portion of the solution is withdrawn into a medicine
dropper provided with platinum-wire electrodes as
shown in the figure. The potential difference between
FIG. VI, 3, 4. the two electrodes is determined before and after the
addition of each increment of reagent. After each
reading near the end point the sheltered solution is forced into the main
volume of solution and the e.m.f. measured. The graph of e.m.f.
readings against volume resembles Fig. VI, 3, 2.
A. Neutralisation reactions.-The indicator electrode may be a hydro-
gen, glass, antimony, or quinhydrone electrode (in the last case the
acid is placed in the beaker and the base in the burette); a calomel
electrode is generally employed as the reference electrode.
The accuracy with which the end point can be found potentio-
metrically depends upon the magnitude of the change in e.m.f. in the
neighbourhood of the equivalence point, and this depends upon the
Potentiometric Titration Methods .' 691
concentration and the strength of the acid and alkali (compare Sections
I, 33-38). Satisfactory results are obtained in all cases except: (a)
those in which either the acid or the base is very weak (K < 10-8 )
and the solutions are dilute, and (b) those in which both the acid and
the base are weak. In the latter case an accuracy of about 1 per cent
may be obtained in O'IN solution.
The method may be used to titrate a mixture of acids which differ
greatly in their strengths, e.g., acetic and hydrochloric acids; the
first break in the titration curve occurs when the stronger of the two
acids is neutralised, and the second when neutralisation is complete.
For this method to be successful, the two acids or bases should differ
in strength by at least 10 5 to 1.
B. Oxidation-reduction reactions.-The theory of oxidation-reduction
reactions is given in Sections I, 48-49. The determining factor is the
ratio of the concentrations of the oxidised and reduced forms of certain
ion species. For the reaction:
Oxidised form + n electrons ~ Reduced form
the potential E acquired by the indicator electrode at 25 C. is given
by:
E = EO + 0.0591 10 [Ox]
n g [Red]
where EO is the standard oxidation potential of the system. The
potential of the immersed electrode is thus controlled by the ratio of
these concentrations. 'During the oxidation of a reducing agent or
the reduction of an oxidising agent the ratio, and therefore the potential,
changes more rapidly in the vicinity of the end point of the reaction.
Thus titrations involving such reactions (e.g., ferrous iron with potas-
sium permanganate or potassium dichromate or ceric sulphate) may be
followed potentiometrically and afford titration curves characterised
by a sudden change of ,WJtential at the equivalence point. The
indicator electrode' is usually a bright platinum wire or foil, and the
oxidising agent is generally placed in the burette.
C. Precipitation reactions.-The theory of precipitation reactions is
given in Sections I, 39-41. The ion concentration at the equivalence
point is determined by the solubility product of the sparingly soluble
material formed during the titration. In the precipitation of an ion I
from solution by the addition of a suitable reagent, the concentration
of I in the solution will clearly change most rapidly in the region of the
end point. The potential of an indicator electrode responsive to the
concentration of I will undergo a like change, and hence the change
can be followed potentiometrically. Here one electrode may be a
saturated calomel or, less conveniently, a hydrogen electrode, and the
other must consist of one which will readily come into equilibrium with
one of the ions of the precipitate. For example, in the titration of
silver ions with a halogen (chloride, bromide, or iodide) this must be a
silver electrode. It may consist of a silver wire, or of a platinum
wire or gauze plated 'with silver and sealed into a glass tube. Since a
halide is to be determined, the salt bridge must be a saturated solution
of potassium nitrate. Excellent results are obtained by titrating
silver nitrate solution with thiocyanate ions.
692 Quantitative Inorganic Analysis
VI, 4. Potentiometric titrations.-Simplified electrode systems anil
methods. The elimination of the troublesome standard reference
electrode of the calomel or metal~salt type and the provision of a
continuous-reading instrument to replace the slide-wire potentiometm
would clearly render the determination of end points (the main purpose
of potentiometric titrations) a more facile procedure than with the
classical set-up. The polarised mono-metallic system and the bi-
metallic self-polarising system have been developed, particularly for
oxidation-reduction work. The former consists of two identical pure
platinum mres, one polarised anodically and the other cathodically
with a polarising current of the order of microamperes; these appear
to behave as two dissimilar metals, and their single electrode potentialE
respond in a different manner. At all events a sharp polarisation
phenomenon is apparent at the equivalence point, and if the potential
difference between the electrodes is plotted against the volume 01
reagent added, the usual differential type of curve is obtained. The
potential difference developed at the end point may be of the order oj
100-200 millivolts.
Foulk and Bowden (1926) introduced the dead-stop technique with
polarised metallic electrodes, and thus rendered the system continuom
reading. The following discussion should assist the reader in appre-
ciating the underlying principles. When a small e.m.f. is applied to a
pair of identical platinum electrodes dipping into a solution containing
no depolarising substances, little or no current flows. This may be
due to the formation of adsorbed layers of hydrogen and oxygen upon
the cathode and anode respectively. The electrodes are thus polarised,
and current cannot flow unless the depolarisation of both is effected.
The fundamental requirement of the dead-stop technique (as opposed
to other methods employing bimetallic systems) is the small potential
difference between the electrodes. This low potential is balanced by
the back e.m.f. of polarisation, hence no current flows, and a galvan-
ometer in the circuit remains undeflected. Under these conditions thE
dead-stop end-point method of titration is applicable to all systems in
which a sharp transition from the polarisation (or depolarisation) of at
least one electrode to the complete depolarisation (or polarisation) oj
both coincides mth the end point of the reaction. Thus in the deter-
mination of sodium thiosulphate by titration with iodine solution,
the thiosulphate acts as an anode depolariser :
28 23-- + H 20 + = 8 46-- + 20H-
: Upon the addition of iodine solution, iodide is formed which can also
act as an anode depolariser. Immediately the equivalence point iE
reached, the free iodine will act as a cathode depolariser :
12 + 2H = 21 - + 2H i-
current will now commence to flow, and the end point is thus indicated
by the sudden commencement of flow of current (and therefore galvan
ometer deflection) through the solution. Thus no current flows through
the galvanometer until the end point is reached, which is indicated by
a permanent deflection of the galvanometer index. Owing to thE
momentary production of high local concentrations, each addition oj
the reagent near the end point may cause the galvanometer index tc
move temporarily from its zero position. This effect, which dependE
Potentiometric Titration Methods 693
upon the rate of titration and the efficiency of stirring, is due to partial
depolarisation of the cathode, and its magnitude often provides a useful
warning of the approach of the end point. In the reverse titration,
i.e., when a solution of iodine (which contains iodide) is titrated with a
solution. of thiosulphate or arsenite, the character of the end point is
reversed. Both electrodes are depolarised, and consequently until
almost to the end point, the galvanometer index will be deflected off
the scale. When the equivalence point is reached, all the iodine will
have been removed and the cathode becomes polarised; the galvan-
ometer index returns to zero, and remains so even after an excess of
titrant has been added. The dead-stop technique may be carried out
with the simple apparatus shown in Fig. VI, 4, 1. G is a galvanometer
of sensitivity of 50-200 mm. per mi-
croampere, B is a 2-volt accumulator G
or a single dry cell, Rl is a high re-
R,
sistance, usually 100,000 ohms, and
R2 is a resistance or potenJ,iometer of
value between 1 and 2 per cent of
R l . The latter should preferably be
a radio potentiometer, which can be
adjusted so that the galvanometer is
brought to zero when at least one
R,
B
I
electrode is polarised, e.g., by dipping
it into a solution of sodium thiosul-
phate. * The mechanical stirrer, which FIG. VI, 4, 1.
is essential, is not shown in the figure.
The essential feature is the adjustment of the two resistances so that
the potential difference between the two electrodes is 10-15 millivolts, -,
just sufficient to balance the back e.m.f. It is advisable to provide the
galvanometer with an adjustable shunt, thus enabling the sensitivity
to be reduced when conditions likely to cause a large flow of current
are encountered. The Cambridge titration apparatus (potentiometric
pattern), Fig. VI, 3, 3, includes a pair of platinum electrodes, and is
particularly suitable for determinations depending upon the dead-stop
end point. The galvanometer may be replaced by a valve system
(compare Mullard-B.T.L. apparatus, Fig. VI, 4, 2) which supplies the
polarising e.m.f. and serves to detect the end point.
The mode of action of the bimetallic system will be apparent from the
following considerations. Noble metals, like platinum or gold, behave
as indicator electrodes in oxidation-reduction reactions in solution.
If an electrode material could be found (e.g., tungsten) which would not
respond to a change of electron activity in solution, it could be em-
ployed as a reference electrode in potentiometric titrations. If the
indicator electrode and the "inert" electrode are placed in the same
* The following were used by the author and gave satisfactory results: G a Tinsley
galvanometer, type SSI, of 49 ohms resistance and a sensitivity of 52 mm.jmicroampere;
Rl a 100,000 ohms carbon resistance (Erie Resister, Ltd., Carlyle Road, The Hyde,
London, N.W.9); and R2 a 2500 ohms wire-wound variable resistance (Colvern, Ltd.,
l\Iawneys Road, Romford, Essex) or a 2200 ohms carbon variable resistance (Centralab).
A 20 ohms variable resistance E3 (A_ F_ Bulgin and Co., Ltd., Bye Pass Road, Barking,
Essex) should be placed in parallel with the galvanometer to act as a sensitivity control
during the initial stages of the titration.
The components (excluding the galvanometer) are conveniently mounted in a small
box; the latter is provided with a panel to house the controls for R2 and E 3, and terminals
for the electrolytic cell, 2-volt accumulator, and galvanometer.
694 Quantitative Inorganic Analysis
solution, then the change of the e.m.f. of such a cell would be the same
as the variation in potential of the indicator electrode during the.
titration. Such a system is termed a bimetallic electrode system.
With these systems the e.m.f. is quite small initially, and does not
increase considerably until the titration is within 02- 03 ml. of the
equivalence point. A slight rise in e.m.f. gives warning ofthe approach-
ing end point, and at the equivalence point there is a very sharp change
of e.m.f. which may be of the order of 01- 0,2 volt. The most satis-
factory combination for oxidation- reduction titrations is platinum-
tungsten. For a number of acid- base titrations the combination of
tungsten with natural graphite, copper, nickel, cobalt, silicon, or silver
are frequently applicable; it is necessary, however, to test the bi-
metallic pair. with each type of acid and base used, and consequently,
the procedure has not become popular for neutralisation reactions.
FIG. VI, 4, 2.
H.T.+
FIG. VI, 4, 3.
B+]OOV.. RE GULATED
VOLTAGE TRANSFORMER
AND VOlT~~EB:SEGULAT'NG +----4:,_-____ _J
FIG. VI, 4, 6.
/80 2
12 + 802 + 3CsH sN + H 0
2 -+ 2C sH sN'HI + CsHsN"6 (A)
..
CALCIUM" 1
CHLORIDE
TOWER
--=====~
DETACHABLE CALCIUM
CHL ORI DE TUBE
STANDARD SOLUTION OF
FISCHER REAGENT
WATER IN METHYL ALCOHOL
FIG. VI, 5, I.
FIG. VI, 5, 2.
FIG. VI, 5, 3.
colour approaches a yellow-brown. Then con-
tinue the addition drop-wise until the galvano-
meter index is on the scale and eventually
returns to the zero position. Run out th'e
solution , deliver another 400 or 500 ml. of the
Fischer reagent into the vessel and titrate as
before. Repeat until two successive titrations
do not differ by more than 001 ml.
T he Cambridge titration apparatus (potentiometric
pattern), Fig. VI, 3, 3, is well adapted for Karl
Fischer-determinations using the dead-stop end
point. The auxiliary apparatus is shown in Fig.
VI ,5, 2. It comprises: two 250-ml. reservoir
burettes, one for the Fischer reagent and the
other for the standard water-in-methanol solu-
t ion; a coned stopper with ground joint to
accommodate the two burette tips, the double
platinum electrodes and the stirrer; I50-ml.
flask with B34 ground joint, and supporting ring
with spring suspension. Each burette is gradu-
ated to 20 ml. in 005 ml. ; the reservoir is closed
by a drying-tube charged with silica gel to
prevent absorption of atmospheric moisture.
The Mullard- B.T.L. Karl Fischer apparatus *
utilises their potentiometric titration apparatus
with magic-eye indicator (Fig. VI, 4, 2) for the
determination of the end point and t he usual
pair of platinum electrodes. The essential
features of the apparatus will be evident from FIG. VI, 5, 4.
* Supplied by Baird and Tatlo ck (London), Ltd., Freshwater Road, Chadwell Heath,
Essex, England.
AA
706 Quantitative Inorganic Analysis
Fig. VI, 5, 3; the complete apparatus is shown in Fig. VI, 5, 4.
The two 25-ml. burettes may be filled from the respective reservoirs
holding 1 litre of the Fischer reagent and the standard water-in-
methanol solution. Magnetic stirring is provided for the titration
cell, and the speed of stirring by means of the iron core sealed in glass
is controlled by a rheostat; difficulties arising with stirrers operated
through the neck of the titration cell are thus avoided.
VI, 6. Some applications of the Karl Fischer reagent.-It is usual to
add an inert solvent, such as dry methanol, in which both the sample
and the reaction products are soluble in order to secure satisfactory
end points; for some compounds the finely powdered solid must be
suspended in the inert solvent and the suspension kept well stirred
during the titration. Generally macro samples should contain 25-250
mg. of water, and the volume of solvent, when employed, is 25-50 ml.
The determination may be checked by adding a known weight of water
and carrying out a duplicate titration.
The following types of organic compounds, as well as many others
which will not be described, have been studied.
Organic acids. These include oxalic acid dihydrate, malonic, citric,
and tartaric acids. Esterification due to the presence of methanol is
not appreciable for acetic and formic acids if the titration is carried
out rapidly; for these acids it is best to use a mixture of equal volumes
of dry methanol and dry pyridine as solvent.
Alcohols. The Karl Fischer titration is generally applicable, and
is superior to density measurements for methanol, ethanol, and
glycerol.
Esters. These include methyl formate, methyl and ethyl acetates,
and methyl and ethyl sulphates; the alkyl sulphates must be dissolved
in 5-10 volumes of anhydrous methyl alcohol for satisfactory end
points.
Lactones, acetals, and ethers.
Hydrocarbons. These include benzene and cydohexane. When the
water content is very low, as in n-hexane, it is best to extract with
pure ethylene glycol, which is usually immiscible with the hydrocarbon.
In this manner it is possible to determine the equilibrium moisture
in hexane after treatment with various desiccants; the results are
collected in the following table:
Equilibrium, Equilibrium,
Desiccant. Water in Hexane, Desiccant. Water in Hexane,
p.p.m. p.p.m.
CaCI 2 , fused 197 Al 2 0 3 002
CaCI 2 , granular os KOH, fused 001
NaOH, fused 09 P2 0 5 00001
Total Volume
Added (mI.). E (mv.). t:J.EjOl mI.
'. 410 435
420 445 10
430 457 12
440 472 15
445 484 24
446 499 15
447 588 89
449 618 15
460 638 18
470 648 10
The nature of the results which may be expected will be evident from the
data presented in the accompanying table. The maximum change per
01 ml. of the reagent added occurs after the addition of 447 ml. of the
solution, and this is accordingly the end point of the titration.
EXPERIMENT 2. Oxidation-reduction reactions. A typical exercise
is the titration of an iodide solution with standard potassium perman-
ganate solution: .
2Mn04 - + 16H+ + 101- -+ 2Mn++ + 8H20 + 512
If A.R. potassium iodide is employed, the reaction may be utilised for
the standardisation of potassium permanganate solution.
Prepare a ca. OlN -potassium permanganate solution. Place
03320 g. (0002 mol.) of dry A.R. potassium iodide and 100 ml. of
02-03N-sulphuric acid in the beaker (Fig. VI, 3, 1). Use a saturated
calomel electrode as reference electrode and a bright platinum wire as
the indicator electrode. Determine the end point as in Experiment 1,
but allow about 1 minute to elapse, when near the equivalence point,
after each addition of the reagent before measuring the e.m.f. Calculate
the normality of the potassium permanganate solution.
EXPERIMENT 3. Precipitation reactions. The indicator electrode must
be reversible to one or the other of the ions which is being precipitated.
Thus in the titration of a potassium iodide solution with standard
silver nitrate solution, the electrode must be either a silver electrode
or a platinum electrode in the presence of a little iodine (best introduced
by adding a little of a freshly prepared alcoholic solution of iodine),
i.e., an iodine electrode (reversible to 1-). The exercise recommended
is the standardisation of silver nitrate solution with pure sodium
chloride.
Prepare an approximately OlN -silver nitrate solution. Place 01169
g. of dry A.R. sodium chloride in the beaker, add 100 ml. of water, and
stir until dissolved. Use a silver-wire electrode (or a silver-plated
platinum wire), and a silver-silver chloride or a saturated calomel
reference electrode separated from the solution by a saturated ammon-
ium nitrate or potassium nitrate-agar bridge. Titrate the sodium
chloride solution with the silver nitrate solution following the general
procedure described in Experiment 1; it is important to have efficient
stirring. Continue the titration to 5 ml. beyond the end point. Deter-
710 Quantitative Inorganic Analysis
mine the end point and thence the normality of the silver nitrate
solution.
EXPERIMENT 4. Dead-stop end-point method of titration. Fit up the
apparatus depicted in Fig. VI, 4, 1,* using clean platinum wire elec-
trodes and a suitable sensitive galvanometel' (e.g., of the Cambridge
spot type). Prepare a OlN -sodium thiosulphate solution and also
a O'lN -iodine solution containing potassium iodide in OlN concentra-
tion. Place 50 ml. of the thiosulphate solution in a 250- or 400-ml.
beaker in which the electrodes t are supported and also provided with
a mechanical stirrer. Adjust the galvanometer spot to zero with the
aid of the R2 potentiometer. Add the iodine solution slowly and with
stirring. The galvanometer spot will remain at zero during most of
the titration; the equivalence point is indicated by the first permanent
displacement of the galvanometer index. The galvanometer deflection
will be increased by further addition of the iodine solution. Note the
volume of the iodine solution added, and compare it with the value
obtained by direct titration with starch indicator.
Repeat the experiment with iodine solution in the beaker and the
thiosulphate solution in the burette. The galvanometer spot must
first be adjusted to zero with both electrodes dipping into sodium
thiosulphate solution. It will be noted that at the commencement of
the titration the galvanometer spot will be off the scale (it is advisable
to use a galvanometer shunt to bring it just on the scale). Near the
end point the displacement will gradually decrease in magnitude (if a
shunt is employed it should be cut out of cir(mit at this stage). With
successive drops of the thiosulphate solution, the rest point of the
galvanometer spot will approach the zero :position, and may make
temporary excursions towards the zero of the scale, until, at the end
point, it will come to rest at or near the zero. Further addition of the
thiosulphate solution has no effect upon the position of the galvano-
meter spot.
The thiosulphate solution may be replaced by O'lN -sodium arsenite
solution, and thus provide an alternative exercise.
EXPERIMENT 5. Use of a commercial thermi.onic valve titrimeter. The
experimental details to be given below refer to the Mullard-B.T.L.
potentiometric-titration apparatus (Fig. VI, 4, 2), but can be readily
adapted to any other commercial titrimeter (e.g., the Fisher electro-
metric titrimeter, Fig. VI, 4, 5). The e.mJ. Ulay be measured with the
aid of the magic-eye balance-point indicator. Excellent practice may
be obtained by determining the ferrous-ion C()llcentration of a solution
by titration with standard potassium dichromate solution.
Prepare 250 ml. of O'lN-potassium dichromate solution (using the
dry A.R. solid) and an equal volume of ca. OlN-ferrous ammonium
sulphate solution; the latter must contain flufficient dilute sulphuric
acid to produce a clear solution, and the exact weight of A.R. ferrous
ammonium sulphate employed should be noted. Place 25 ml. of the
ferrous ammonium sulphate solution in the beaker, add 25 ml. of ca.
5N-sulphuric acid and 50 ml. of water. Charge the burette with the
O'lN-potassium dichromate solution. Use the special saturated
calomel electrode (Fig. VI, 4, 4) provided with the apparatus; place
* The commercial apparatus, Fig. VI, 3, 3 may be uSed, if available.
t The platinum electrodes should be thoroughly cl"'aned by immer&ion in boiling
concentrated nitric acid and then thoroughly washed with distilled water.
Potentiometric Titration Methods 711
saturated potassium chloride solution in the cup, fill the long capillary
with the solution, wipe off the excess of solution from the tip with
filter-paper, and clip the electrode into position in the titration stand.
Use a bright platinum electrode as the indicator electrode. Set the
stirrer in motion. Proceed with the titration as directed in Experiment
1. After each addition of -the dichromate solution measure the e.m.f.
of the cell. Determine the end point: (i) from the potential-volume
curve and (ii) by the differential method. Calculate the normality
of the ferrous ammonium sulphate solution, and compare this with the
value computed from the actual weight of solid employed in preparing
the solution.
Repeat the experiment using another 25 ml. of the ferrous ammonium
sulphate solution but with a pair of polarised platinum electrodes;
the latter are prepared with the aid of the special polarising switch
provided on the apparatus. The first permanent deflection of the
magic-eye indicator gives the end point. The experiment may also be
repeated with the tungsten electrode (reference) and the platinum
electrode (indicator) pair.
Numerous other determinations can, of course, be made by potentio-
metric titration. The reader is referred to the Bibliography (particularly
Nos. 1, 2, 3, 5, 6, 7, and 8) in Section VI, 12 for further information.
A few typical determinations are given in Sections VI, 8 to VI, 11.
VI, 8. Standardisation of sodium thiosulphate or of iodine solution
with potassium permanganate or with potassium dichromate.-This and
the succeeding experiments are best carried out with a commercial
apparatus such as the Cambridge titration apparatus (potentiometric
pattern, Fig. VI, 3, 3) or a thermionic-valve titrimeter. The brief
experimental details apply to the former type of apparatus, but can be
readily adapted to the apparatus which employs a magic-eye indicator
for the determination of the end point. The mode of calculation of
the result will be self-evident in the examples given, or will have
been described in an earlier chapter.
Place, say, 25 ml. of the. standard potassium permanganate or the
standard potassium dichromate solution (ca. O'OIN) in the beaker, add
about 100 ml. ofO2-05N-sulphuric acid and excess of potassium iodide.
Stir the mixture and allow the reaction to proceed for 5-10 minutes.
Adjust the galvanometer spot to one end of the scale and introduce
the sodium thiosulphate solution from a burette until the spot returns
almost to zero, this being the end point: one further drop may be
added, and no change in the rest position of the spot should be observed
after it has come to rest. The concentration of the sodium thiosulphate
solution may now be calculated.
Now introduce, say, 25 ml. of the iodine solution and 100 ml. of
02-05N-sulphuric acid into the beaker, and carry out the titration
with the now-standardised sodium thiosulphate solution as before.
Calculate the normality of the iodine solution.
Note. Titrations may be carried out in dilute solution (up to, say,.
2 X 10-3N) by the addition of sufficient potassium iodide solution (e.g., 5 ml.
of a 10 per cent solution) to depolarise the anode.
VI, 9. Determination of the available chlorine in bleaching powder,
etc.-Triturate a known weight of the bleaching powder in a clean glass
mortar with a little water, and make up to a known volume with the
~ U,U;'W~H.LWVe, 1 norgan~c Anays~8
For initial practice in the method the student may determine the
manganese content of anhydrous A.R. manganous sulphate. Heat
A.R. manganese sulphate crystals to 280 0 , allow to cool, grind to a fine.
0
powder, reheat at 280 for 30 minutes, and allow to cool in a desiccator.
Weigh accurately about 22 g. of the anhydrous manganous sulphate,
dissolve it in water and make up to 250 ml. in a volumetric flask.
Prepare a 0'02M solution of potassium perI1langanate and standardise
it against A.R. sodium oxalate or A.R. arsenious oxide.
714 Quantitative Inorganic Analysis
Prepare 5N -sodium hydroxide solution using the A.R. solid: test a
10-ml. sample for reducing agents by adding a drop of the permanganate
solution; no green coloration should develop.
Prepare also a saturated solution of the purest available sodium
pyrophosphate (do not heat above 25 C., otherwise appreciable hydro-
lysis may occur); 12 g. of the hydrated solid Na 4 P 2 0 7 ,lOH 2 0 will
dissolve in 100-150 ml. of water according to the purity of the com-
pound. It is essential to employ freshly made sodium pyrophosphate
solution in the determination.
Place 150 ml. of the sodium pyrophosphate solution in a 250-400-
ml. beaker, adjust the pH to 6-7 by the addition of concentrated
sulphuric acid from a I-ml. graduated pipette (use the appropriate
indicator test-paper or a glass electrode). Add 25 ml. of the mangan-
ous sulphate solution and adjust the pH again to 6-7 by the addi-
tion of 5N -sodium hydroxide solution. Introduce a bright platinum
electrode into the solution, aI1d connect the latter through a saturated
potassium chloride bridge to _a saturated calomel electrode; complete
the assembly for potentiometric titration as in Fig. VI, 3, 1. (The
Mullard-B.T.L. potentiometric titration apparatus, Fig. VI, 4, 2, or
an equivalent apparatus, may also be used.) Stir the mixture, add
the potassium permanganate solution in 2-ml. portions at first, reduce
this to OI-ml. portions in the vicinity of the end point: determine
the potential after each addition. Plot the e.m.f. values (ordinates)
against the volume of potassium permanganate solution added (ab-
scissro), and determine the equivalence point. From your curve read
off the potential at the equivalence point; this should be + 047 volt.
In the determination the permanganate ion undergoes only a 4-electron
change to the + 3 state, hence a O02M solution is OOSN. Calculate
the percentage of Mn in the sample.
1 m!. 0'02M-KMn0 4 := 000439 g. Mn
Repeat the titration using polarised platinum electrodes and the
magic-eye indicator (Fig. VI, 4, 2); the end point is readily detected.
Further practice may be obtained by determining manganese in a
manganese ore and in a steel.
Pyrolusite. Dissolve 15-2 g., accurately weighed, of pyrolusite *
in a mixture of 25 ml. of 1 : 1 hydrochloric acid and 6 ml. of concentrated'
sulphuric acid, and dilute to 250 ml. Filtration is unnecessary.
Titrate an aliquot part containing SO-100 mg. of manganese: add
200 ml. of freshly prepared, saturated sodium pyrophosphate solution,
adjust the pH to a value between 6 and 7, and perform the potentio-
metric titration as described above.
Steel. Dissolve 5 g., accurately weighed, of a steel t in 1 : 1 nitric
acid with the aid of the minimum volume of hydrochloric acid in a
Kjeldahl flask. Boil the solution down to a small volume with excess
of concentrated nitric acid to re-oxidise any vanadium present reduced
by the hydrochloric acid: this step is unnecessary if vanadium is known
to be absent. Dilute, boil to remove gaseous oxidation products,
allow to cool, add 1 g. of urea or sulphamic acid, and dilute to 250 ml.
Titrate 50-ml. portions as above.
* Either Ridsdale's "Pyrolusite Mn Ore (dry)" or Bureau of Analysed Samples
" Manganese Ore" (a British Chemical Standard) is suitable.
t l!se either Ridsdale's "Medium Carbon Steel" or Bureau of Analysed Samples
" Carbon Steel R " or British Standard Steel Sample, No. 11.
Potentiometric Titration Methods 715
VI, 13. Determination of cobalt.-Cobaltous salts may be titrated
potentiometrically by making use of the reaction with standard
O'IN(O'IM)-potiLssium ferricyanide solution in the presence of a high
concentration of ammonium citrate and of ammonia solution. The
reactants should preferably be covered with a layer of an immiscible
solvent (e.g., petroleu!ll ether, b. p. 100-120 C.); this serves to exclude
air, shields the operator and equipment from the strongly ammoniacal
vapours, and minimises the formation of incrustations on the burette
tips: efficient mechanical stirring is essential. The cobaltous salt
solution (e.g., cobaltous sulphate) of approximately 005M concentration
should be placed in the burette: this may be prepared from pure cobalt
or fro.m a pure co.balt salt, and its co.ncentratio.n may be checked against
the standard po.tassium ferricyanide so.lution o.r by a gravimetric
metho.d (as anthranilate, etc.-Sectio.n IV, 33). If a small co.ncentra-
tio.n of co.balt is to. be determined, the CDbalt so.lutio.n may be added to.
excess of standard pDtassium ferricyanide so.lutio.n, etc., and then:
titrated with the standard co.balto.us so.lutio.n: a simple calculatio.n
will give the cDbalt co.ntent o.f the unkno.wn so.lutio.n.
Nickel, c9Pper, chrQmium, tungsten, and mQlybdenum do. nQt interfere,
and irQn in cQncentratiQn up to. Qne-twentieth o.f the amQunt Qf cQbalt
is withQut effect; manganese must be remQved befQre the titratiQn is
cQmmenced, fQr it is said to. be quantitatively Qxidised to. the trivalent state.
To. o.btain experience in the titratiQn the student may employ a
0'0511f-cDbalt sulphate so.lutiDn prepared fro.m uneffio.resced crystals o.f
the A.R. heptahydrate. Alternatively, a sample o.f co.balt ammo.nium
sulphate Co.S04,(NH4)2S04,6H20 (prepared by mixing cQncentrated
so.lutiDns o.f the Co.mpDnent sulphates in equimDlecular propo.rtiQns and
crystallising) may be used. A useful check is pro.vided by a gravi-
metric determinatio.n of the co.balt cDntent (Sectio.n IV, 33).
Prepare the fo.llo.wing so.lutio.ns :
Standard O05N(O05M)-potassiumferricyanide. Finely pDwder abDut
20 g. of A.R. po.tassium ferricyanide (mDlecular weight = 32925),
dry at 60-80 C., and allDw to. co.o.l in a desiccato.r. Weigh o.ut 1646 g.
of the dry so.lid, disso.lve it in water, and dilute to. 1 litre in a standard
flask. Check the nDrmality o.f the potassium ferricyanide so.lutiDn by
io.dometric titratio.n (Sectio.n III, 120) using so.dium thio.sulphate
so.lutiDn which has been standardised against pure po.tassium io.date.
Ammonium citrate sDlution. Disso.lve 50 g. o.f pure citric acid in
100 ml. Df water and add 675 ml. Df cDncentrated ammo.nia so.lutio.n
(sp. gr. 0'88).
Procedure. Into. a 250- o.r 400-ml. beaker place 25 ml. Df the 005N-
po.tassium ferricyanide so.lutiDn, 10 ml. o.f the ammo.nium citrate
so.lutiDn and 100 ml. o.f ca. 5N-ammo.nia so.lutio.n (prepared by diluting
30 ml. o.f cDncentrated ammDnia so.lutio.n to. 100 ml. with distilled
water). Co.ver the resulting solutio.n with a layer o.f 25 ml. o.f light
pet4:'o.leum, b.p. 100-120 C. Intro.duce a bright platinum' and a
saturated calo.mel electro.de and also. a glass stirrer into. the so.lution;
use the Mullard-B.T.L. po.tentiDmetric titratio.n apparatus (Fig.
VI, 4, 2) or an equivalent apparatus. Read the po.tential between the
platinum and calo.mel electrDdes with the aid o.f the magic-eye indicatDr
after each additio.n of apprDpriate vo.lumes (1-2 ml.) o.f the co.balto.us
sulphate (o.r co.balto.us ammo.nium sulphate) sDlutiDn fro.m the burette.
The po.tential falls fro.m an initial value of about 300 millivolts (po.sitive
, .LV "tU;WIHHUHve 1 nUTgan~c .Analy8~8
to S.C.E.) and falls slowly to within 05-1 m!. of the end point. When a
reading of about 100 millivolts has been attained, add the cobalt
sulphate solution dropwise, and allow sufficient time for the potential
to become steady before proceeding to the next addition. The end
point is sharp and is easily deduced from the potential (E) /volume of
solution (Vx) graph or, better, by plotting dEjclV against Vx (see
Section VI, 7). Immediately after the end point has been passed, the
readings become negative VS. S.C.E., and if a complete titration curve
is required a reversing key should be included in the circuit; this is
usually unnecessary, as the end point is attained before the reversal of
polarity occurs.
Calculate the strength of the cobalt sulphate solution from the known
normality of the potassium ferricyanide solution.
Dilute the standard solution of the cobalt salt n-fold, introduce a
known volume of this diluted solution into a 400-ml. beaker, and
repeat the titration exactly as detailed above. Calculate the concentra-
tion of the diluted solution from the new value of the end point, and
compare t;his figure from that deduced from the dilution factor (n).
Potentiometric Titration Methods 717
718
Conductometric Titration Methods 719
dilution of the cation and anion respectively. The mobilities of some
ions in water at 25 C. are collected in Table 1.
TABLE I.-MOBILITY OF SOME IONS AT INFINITE DILUTION AT 25 0
c.
Cation. I~. Anion . I':.
H+
. 3498 OH- 1985
Na+ 501 CI- 763
K+ 735 Br- 784
Li+ 387 1- 768
NH/ 734 NO a - 714
Ag+ .
TIl- . 619
747
CI0 4 -
HCO a -
680
445
1/2 CaH 595 CH3 COO- 409
1/2 Sri-+ 595 CH aCH 2COO- 358
1/2 BaH 636 1/2 S04-- 798
1/2 MgH 531
The increase of mobility of most ions is about 2 per cent for each 10 C.
rise in temperature. It is therefore important to allow the contents
of the conductivity cell to attain thermal equilibrium before proceeding
with the conductance measurement. The conductance of weak electro-
lytes is largely dependent upon the degree of ionisation, which is itself
also dependent upon the temperature.
The addition of an electrolyte to a solution of another electrolyte
under conditions producing no appreciable change in volume will affect
its conductance according as to whether or not ionic reactions have
occurred. If no ionic interaction takes place, such as in the addition
of one simple salt to another (e.g., potassium chloride to sodium nitrate),
the conductance will rise. If ionic interaction does occur l as in the
addition of a base to an acid, the conductance will decrease owing to
the replacement of the hydrogen ion (high mobility) by a metallic ion
(lower mobility). This is the principle underlying conductometric
titrations, i.e., the substitution of ions of one mobility by ions of another
mobility.
Let us consider how the conductance of a solution of a strong electro-
lyte A +B- will change upon the addition of a reagent aT D-, assuming
that the cation A + (which is the ion to be determined) reacts with the
ion D- of the reagent. If the product of the reaction AD is relatively
insoluble or only slightly ionised, the reaction may be written:
A+B- + a+D- ~ AD + a+B-
Thus in the reaction between A + ions and D- ions, the A + ions are
replaced by a+ ions during the titration. As the titration proceeds
the conductance increases or decreases, depending upon whether the
mobility of the a+ ion is greater or less than that of the A + ion.
During the progress of neutralisations, precipitations, etc., changes
in conductivity may, in general, be expected, and these may therefore
be employed in determining the end points as well as the progress of
the reactions. The conductivity is measured after the addition of
each increment of the reagent, and the points thus obtained are plotted
to give a graph which consists of two straight lines intersecting at the
equivalence point. The accuracy of the method is greater the more
acute the angle of intersection and the more nearly the points of the
,..,v "t'uanrnatwe lnorgamc Analysis
graph lie on a straight line. The volume of the solution should not
change appreciably; this may be achieved by employing a titrating
reagent which is 20 to 100 times more concentrated than the solution
being titrated, and the latter should be as dilute as practicable. Thus
if the conductivity cell contains about 100 m!. of the solution at the
beginning of the titration, the reagent (say, of fifty times the concentra-
tion of the solution being analysed) may be placed in a 5-ml. micro-
burette, graduated in 001 or 002 ml. A correction for the dilution
effect may, however, be made by multiplying the values, of the specific
conductance by the factor (V + v)/V, in which V is the original volume
of the solution and v is the volume of reagent added.
In contrast to potentiometric titration methods (see Chapter VI)
but similar to amperometric titration methods (see Chapter IX),
measurements near the equivalence point have no special significance.
Indeed, owing to hydrolysis, dissociation, or solubility of the reaction
product, the values of the conductivity measured in the vicinity of the
equivalence point are usually worthless in the construction of the graph,
since one or both curves will give a rounded portion at this point.
Even if the conductivity of the reaction product at the equivalence
point is appreciable, the reaction may frequently be employed for
conductometric titration if the conductivity of the reaction product
AD is practically completely suppressed by a reasonable excess of
A + or B-. Thus conductometric methods may be applied where visual
or potentiometric methods fail to give results owing to considerable
solubility or hydrolysls at the equivalence point, for example, in many
precipitation reactions leading to moderately soluble substances, in
the direct titration of weak acids by weak bases, and in the displace-
ment titration of salts of moderately weak acids or bases by strong
acids or bases. A further important advantage is that the method is
as accurate in dilute as in more concentrated solutions; it can also
be employed with coloured solutions.
The relative change of conductivity of the solution during the
reaction and upon the addition of an excess of reagent largely determines,
the accuracy of the titration; under optimum conditions this is about
05 per cent. Large amounts of foreign electrolytes, which do not take
part in the reaction, must be absent, since these have a considerable
effect upon the accuracy. In consequence, the conductometric method
has much more limited application than visual, potentiometric, or
amperometric procedures.
VII, 2. Apparatus and measurements.-A conductivity cell for
conductometric titrations may be of any kind that lends itself to
thorough stirring (preferably by mechanical means) of the contents and
permits the periodical additions of reagent. It should preferably be im-
mersed in a thermostat controlled to Olo C. or, better, to O'Olo C. ;
if a thermostat is not available, the cell should be immersed in a large,
well-lagged tank of water which has acquired the temperature' of the
laboratory and is gently stirred by mechanical means. The conductivity
cell should be constructed of Pyrex or other resistance glass. The
electrodes should, as a rule, be about 1 sq. cm. in area, and welded to
thick platinum wires that are fused into glass tubes in which they make
contact with mercury; the ends of the copper leads that dip into the
mercury should be previously amalgamated. The distance between
the electrodes will be determined by the change in conductance of the
Conductometric Titration Methods 721
solution being titrated. For low-conductance solutions (e.g., when
extremely dilute), the electrodes should be large and close together.
For precipitation reactions, the electrodes must be vertical. Several
cells with different cell constants (i.e., with different size electrodes and
at varying distances apart) should be available for measurements with
solutions of widely different conductivities. For many purposes a
cell with electrode separation of 2 cm. is satisfactory. The bright
platinum electrodes should be platinised in order to minimise polarisa-
tion effects.
The following procedure may be used for platinising the electrodes. The
conductivity vessel and electrodes are thoroughly cleaned by immersion in a
warm solution of potassium dichromate in concentrated sulphuric acid.
After washing with distilled water until free from acid, the electrodes are
plated from a solution containing 3 g. of chloroplatinic acid and 0025 g. of
lead acetate per 100 m!. The current may be obtained from two accumulators
(4 volts), the poles of which are connected to the ends of a suitable sliding
resistance. The current is adjusted so as to produce a moderate evolution of
hydrogen. Each electrode should be used alternately as anode and cathode
(i.e., the current should be reversed every half minute) and electrolysis
should be continued until both electrodes are covered with a jet-black deposit.
The time may vary from about two to about five minutes. After platinising,
the electrodes must be freed from traces of chlorine by connecting the two
electrodes together as cathode and electrolysing in dilute sulphuric acid,
using another platinum electrode as anode, for about fifteen minutes. The
electrodes are then washed with distilled water and afterwards kept immen,ed
in distilled water until required for use.
A B
c D
FIG. VII, 2, 1.
ends, the cell constant can be determined from the geometrical measure-
ments, i.e., length (cm.)jarea (sq. cm.). It is usual, however, to calcu-
late the cell constant from the measurement of the resistance (or con-
ductance) of a solution of known specific conductance. Potassium
chloride solutions are generally employed, since the specific conduc-
tances of aqueous solutions of this salt have been determined with a
high degree of accuracy at several temperatures (Table II).
For conductometric titrations it is not essential to know the absolute
conductance; it usually suffices to plot the reciprocal of the measured
resistance (which is proportional to the conductance) against the
volume of the reagent added.
The passage of a current through a solution of an electrolyte may
Conductometric Titration Methods 723
TABLE IT.-SPECIFIC CONDUCTANCE, K, OF POTASSIUM CHLORIDE
SOLUTIONS FOR CELL CONSTANT DETERMINATIONS
I
Temperature.
Grams of KCl per 1000 g. of Water.
I
76627. 74789. 074625.
10 008289 0009316 00010151
15 009213 0010460 00011422
18 009784 0011167 00012205
20 010161 0011639 00012731
25 011134 001285() 00014088
30 012127 0014100 00015466
FIG . V II , 2, 3:
H .T . +
F IG . VII, 2, 4.
w
U
z
....
/ uz
....
u u
:J :J
o o
Z Z
o ou
u
u
z
u
Z
,_ ,_
u u
:J
:J o
U
Z Z
o o
u u
I
I
I
EQUIVALENTS NaOH EQUIVALENTS Of AlKALI
(e) (dl
w w
U U
z z
,_ ....
u u
:J :J
o o
Z Z
o
u
o
u
Q R S
ML OF ALKALI SOLUTION EQUIVALENTS NaOH
(el (f)
w
U
u
z
z
,_
,_ u
u :J
:J o
o Z
Z o
o
u
u
EQUIVALENTS
(g) (hi
FIG. VII, 3, 1.
Conductometric Titration Methods 727
Strong acid with a weak base. The titration of a strong acid with a moder-
ately weak base (K ca. 10-5 ) may be illustrated by the neutralisation
of dilute sulphuric acid by dilute ammonia solution (Fig. VII, 3, 1 b).
The first branch of the graph reflects the disappearance of the hydrogen
ions during the neutralisation, but after the end point has been reached
the graph becomes almost horizontal, since the excess of ammonium
hydroxide is not appreciably ionised in the presence of ammonium
sulphate.
Weak acid with a strong base. In the titration of a weak acid with a strong
base, the shape of the curye will depend upon the concentration and
~dissociation constant K of the acid. TJilljg the neutralisation of
acetic acid (K = 08 X 10-5 ) with sodium hydroxIde solutIOn
neutral ~dium acetate) w~-h~i~c~h:.I~s~o~r~m~e~~~~_11.J=--;:u."""_~~~
the titration tends to re ress e ionisati e
presen 1 s con uctance decreases. The rising salt concentra-
tIon will, however, tencrto produce an increase in conductance. In
consequence of these opposing influences thl,) titration curves may have
mjni.mar;--ihe position of which will dep-end upon the concentration and
upon the strength of the weak aCld:- As the titration proceeds, a
somewn.at indefinite break will occur at the end point, and the graph
will become linear after all the acid has been neutralised. Some curves
for acetic acid-sodium hydroxide titrations are shown in Fig. VII,3, 1 c.
For moderately strong acids (K ca. 10-3 ) the influence of the rising
salt concentration is less pronounced, but, nevertheless, difficulty is
also experienced in accurately locating the end point. Thus curve 1
in Fig. VII, 3, 1 d is obtained upon titrating 0'005N-o-nitrobenzoic
acid with 0'130N-potassium hydroxide; the neutralisation line is
slightly curved in the neighbourhood of the end point. Righellato
and Davies (1933) give two procedures for determining the end point
in the titration of weak acids with strong bases. The acid is first
titrated with ammonium hydroxide solution; if the end point cannot
be obtained from the curve with the desired accuracy, a second titration
is carried out using potassium hydroxide solution of the same concentra-
tion. The two curves are practically identical up to the neutralisation
point, and beyond this straight lines are obtained in both titrations,
the intersection of which gives the end point. In Fig. VII, 3, 1 d, '
curve 2 is obtained with 0130N -ammonium hydroxide solution. If
the end point is required with great accuracy, a correction should be
applied for the fact that the conductance of the ammonium salt is
approximately 06 per cent lower than that of the potassium salt
solutions, and the point of intersection should therefore be found when
the final section of curve 2 is raised by this amount.
In the second procedure the titration is commenced with a small
amount of ammonium hydroxide solution (sufficient, say, to neutralise
one-third of the acid), and is then completed with sodium hydroxide
solution of the same concentration. A typical curve for 0'005N-
mandelic acid is shown in Fig. VII, 3, 1 e. When all the acid has been
neutralised the conductance of the mixture falls owing to the replace-
ment of the ammonium ion by the more slowly moving sodium ion
(NH 4lV1+ NaOH ~ NH 4 0H + NalYi) ; when the displacemoot of
the ammonia is complete, the conductivity rises abruptly. At this
end point (8), the total amount of sodium hydroxide solution added
Q8 is equivalent to the acid originally present (PQ represents the first
728 Quantitative Inorganic Analysis
stage of the titration performed with ammonium hydroxide solution).
Alternatively, the acid present is also measured by the total alkali added
to the point at which the conductivity falls, i.e., by P R. A double
check is thus obtained in the titration. The method may be employed
to improve the end point of any titration if the acid is sufficiently strong
to form an ammonium salt.
Very weak acid with a strong base. The initial conductance is very small,
but increases as the neutralisation proceeds owing to the salt formed.
The conductance values near the equivalence point are high because of
hydrolysis; beyond the equivalence point the hydrolysis is consider-
ably reduced by the excess of alkali. To determine the end point,
values of the conductance considerably removed from the equivalence
point must therefore be used. Some titration curves for boric acid
and sodium hydroxide solution are given in Fig. VII, 3, If.
Weak acids with weak bases. The titration of a weak acid and a weak base
can be readily carried out, and frequently it is preferable to employ
this procedure rather than use a strong base. Fig. VII, 3, 1 g is the
titration curve ofO003N-acetic acid with O'0973N-ammonium hydroxide
solution. The neutralisation curve up to the equivalence point is
similar to that obtained with sodium hydroxide solution, since both
sodium and ammonium acetates are strong electrolytes; after the
equivalence point an excess of ammonium hydroxide solution has little
effect upon the conductivity, as its dissociation is . depressed by the
ammonium salt present in the solution. The advantages over the use
of strong alkali are that the end point is more easy to detect, and in
dilute solution the influence of carbon dioxide may be neglected.
Mixture of a strong acid and a weak acid with a strong base. Upon adding a
strong base to a mixture of a strong acid and a weak acid (e.g., hydro-
chloric and acetic acids), the conductance falls until the strong acid
is neutralised, then rises as the weak acid is converted into its salt,
and finally rises more steeply as excess of alkali is introduced. Such a
titration curve is shown as S in Fig. VII, 3, 1 h. The three branches
of the curve will be straight lines except in so far as: (a) increasing
dissociation of the weak acid results in a rounding off of the first end
point, and (b) hydrolysis of the salt of the weak acid causes a rounding
off of the second end point. Usually, extrapolation of the straight
portions of the three branches leads to definite location of the end
points. Here also titration with a weak base, such as ammonium
hydroxide solution, is frequently preferable to strong alkali for reasons
already mentioned in discussing weak acids: curve W in Fig. VII, 3,1 k,
is obtained by substituting ammonium hydroxide solution for the
strong alkali. The procedure may be applied to the determination of
niineral acid in vinegar or other weak organic acids (K {: 10-5 ).
Displacement (or replacement) titrations. When a salt of a weak acid is
titrated with a strong acid, the anion of the weak acid is replaced by
that of the stronger one and the weak acid itself is liberated in the
undissociated form. Similarly, in the addition of a strong base to the
salt of a weak base, the cation of the weak base is replaced by that of
the stronger one and the weak base itself is liberated in the undissoci-
ated form. If, for example, N -hydrochloric acid is added to a O'IN-
solution of sodium acetate, the curve shown in Fig. VII, 3, 2 is
obtained; the acetate ion is replaced by the chloride ion. The initial
increase in conductivity is due to the fact that the mobility of the
Conductometric Titration Methods 729
chloride ion is slightly greater than that of the acetate ion. Until
the replacement is nearly complete, the solution contains sufficient
sodium acetate to suppress the ionisation of the liberated acetic acid
and thereby render negligible its contribution to the conductivity of
the solution. Near the equivalence point the acetic acid is sufficiently
ionised to affect the conductivity, thus leading to higher values of
the conductivity and the rounded portion of the curve. Beyond the
equivalence point when excess of hydrochloric acid is present, the
ionisation of the acetic acid is again suppressed and the conductivity
rises rapidly. It has been calculated by Kalthoff (1941) that to titrate
a O'lN -salt solution the dissociation constant must not be greater than
5 X 10-4 , for a OOlN-salt solution K :;j> 5 X 10-5 , and for a O'OOlN'salt
UJ
U
Z
;:::
U
::J
o
Z
o
u
UJ
U
z
..:
...
u
:::J
a
z
o
u
I
I
I
rA
ML. OF REAGENT
FIG. VII, 3, 3.
"
Oonductometric Titration Methods 733
'.
CHAPTER VIII
POLAROGRAPHY
VIII, 1. GENERAL INTRODUCTION
If a steadily increasing voltage is applied to a cell incorporating a
relatively large quiescent mercury anode and a minute mercury cathode
(composed of a succession of small mercury drops falling slowly from a
fine capillary tube), it is frequently possible to construct a reproducible
current-voltage curve. The electrolyte is a dilute solution of the
material under examination (which must be electro-active) in a suitable
medium containing an excess of an indifferent electrolyte (supporting
electrolyte, or base or ground solution) to carry the bulk of the current
and raise the conductivity of the solution, thus ensuring that the
material to be determined, if charged, does not migrate to the dropping
mercury cathode. From an examination of the current-voltage
curve, information as to the nature and concentration of the material
may be obtained (Heyrovsky, 1922). Heyrovsky and Shikata (1925)
developed an apparatus which increased the applied voltage at a steady
rate and simultaneously recorded photographically the current-voltage
curve. Since the curves obtained with this instrument are a graphical
representation of the polarisation of the dropping electrode, the
apparatus was called a polarograph, and the records obtained. with it,
polarograms. It must be emphasised that, while this (or an equivalent
pen-recording) instrument is valuable in routine determinations as a
time saver, it is by no means essential for polarographic work: excel-
lent results may be obtained by plotting current-voltage curves from
readings obtained with a home-made polarograph (vide infra) or with
.the equivalent commercial apparatus. Throughout this chapter the
term polarogram will be used, irrespective of whether it is recorded
automatically or obtained by plotting a series of individual readings.
The basic apparatus for polarographic analysis is depicted in Fig.
VII I, 1, 1. The dropping mercury electrode is here shown as the cathode
(its most common function); it is sometimes referred to as the indicator
or micro-electrode. The anode is a pool of mercury, and its area is
correspondingly.large, so that it may be regarded as incapable of
becoming polarised, i.e., its potential remains almost constant in a
medium containing anions capable of forming insoluble salts with
mercury (01-, S04--' etc.); it acts as a reference electrode. The
polarisation of the cell is therefore governed by the reactions occurring
at the minute dropping mercury cathode. Inlet and outlet tubes
are provided in the cell for expelling dissolved oxygen from the
solution by the passage of an inert gas (hydrogen or nitrogen) before,
but not during, an actual measurement-otherwise the polarogram of
the dissolved oxygen will appear in the current-voltage curve. P is a
potentiometer by which any e.m.f. up to 3 volts may be gradaally
applied to the cell. S is a shunt for adjusting the sensitivity (f the
galvanometer G appropriate to the nature and concentration LJf the
734
Polarography 735
substance being investigated. It may be mentioned that under these
conditions the current-voltage curve is really a current-cathode
FIG. VIII, 1, 1.
~I
mercury cathode is indeterminate, and ;;;1
21
will assume any potential applied to <I
"SI
it from an external source; when it )';1
1
acquires a potential different from that A
1
I B
which it had in the absence of electrical
APPLIED POTENTIAL (VOLTS)
connexions, the indicator electrode is
said to be polarised. FIG. VIII, 1, 2.
Let us consider what will occur if an
external e.m.f. is applied to the cell shown in Fig. VIII, 1, 1, charged
with, say, a dilute, oxygen-free solution of cadmium chloride. All
the positively charged ions present in the solution will be attracted to the
negative-indicator electrode by: (a) an electrical force, due to the
attrac';ion of oppositely charged bodies to each other, and by (b) a
diffusi', ~ force, arising from the concentration gradient produced at the
electrode surface. The total current passing through the cell can be
736 Quantitative Inorganic Analysis
regarded as the sum of these two factors. A typical simple current-
voltage curve is shown in Fig. VIII, 1, 2. The indicator electrode,
being perfectly polarisable, assumes the correspondingly increasing
negative potential applied to it; from A to B practically no current
will pass through the cell. At B, where the potential of the micro-
electrode is e-qual to the decomposition potential of the cadmium ions
with respect to a metallic cadmium electrode, the current suddenly
commences to increase and the indicator electrode becomes depolarised
by the cadmium ions, which are then discharged upon the electrode sur-
face to form metallic cadmium, consequently a rapid increase in the
current flowing through the cell will be observed. At the point C the ,
current no longer increases linearly with applied potential but a pproache \
a steady limiting value at the point D: no increase in current is observed
at higher cathode potentials unless a second compound able to depolarise
the indicator electrode is present in the solution. At any point on the
curve between Band C (usually spoken of as the polarographic wave) the
number of cadmium ions reaching the micro-electrode surface as a result
of migration and diffusion from the main bulk of the solution always
exceeds the number of cadmium ions which react at and are deposited
upon the electrode. At the point C the rate of supply of the cadmiurl
ions from the main bulk of the solution to the indicator-electrode surface
has become equal to the rate of their deposition. Hence at potentials
more negative than point D, the concentration of undischarged cad-
mium ions at the micro-electrode surface is negligibly small relative to
the cadmium-ion concentration in the bulk of the solution; no further
increase in current passing through the electrolytic cell can be ex~ected,
since the limiting current is now fixed by the rate at which cadmiUlll
ions can reach the electrode surface. '
A numbeJ" of polarisable micro-electrodes (e.g., a rotating platinum wire,
ca. 3 mm. long and 05 mm. diameter, suitably mounted, or stationary
noble-metal electrodes) have been used in determining current-voltage
curves, but the most satisfactory is a slowly gtowing drop of mercury
issuing, under a head of 40-60 cm. of mercury, from a resistance-glast
capillary (005-006 mm. in diameter and 6-7 cm.long) in small, uniform
drops. The dropping mercury electrode has the following advantages :'
(i) its surface is reproducible, smooth, and continually removed; (ii) the "
surface area can be calculated from the weight of the drops; (iii) mer-
cury amalgamates with most metals; (iv) the value of the overvoltage
of hydrogen is highest on mercury, so that much work can be done in
acid solutions and at large negative potentials without disturbance
from the evolution of hydrogen; and (v) the current instantly assumes
a steady value and is reproducible.
Reference has already been made to the convenience for routine
analytical work of using a mercury pool covering the bottom of the
electrolysis cell as the non-polarisable reference electrode. If the solution
covering the mercury pool contains chloride or other similar depolaris-
ing ions of concentration c, the mercury pool acts as a calomel or other
type of reference electrode of approximate concentration c. This
potential, although constant, is not known with accuracy, and must
therefore be determined after each current-voltage experiment by
balancing against some standard half-cell, if a current--electrode
potential curve is required. This additional determination may be
avoided by the use of an external standard-reference electrode con-
Polarography 737
nected to the electrolysis vessel by a salt bridge; a large saturated
calomel electrode is perhaps the most convenient. The potential of
the polarised micro-electrode Em can then be calculated from the
relationship:
Em = Er + V + IR
where Er is the potential of the non-polarisable reference electrode,
V is the applied voltage, I is the observed current, and R is the resis-
tance of the electric circuit. (In polarography it is usual to regard
the current as positive when the micro-electrode is the cathode, and
negative when it is the anode.) The correction fo:t IR becomes necessary
,,-hen the product of the current and the resistance exceeds 1 millivolt.
I
I
:
I 3
DE~:~~N~ 6
: ~
o
m"",, co,,,.., \_______________ J_ _ _
APPLI;D VOLTAGE
where a ox and ared. are the activities of the oxidant and reductant
respectively as they exist at the electrode surface (henceforth called the
electrode-solution interface and denoted by the subscript "i ")/ R
is the gas constant, T the absolute temperature, n the number of ,
electrons involved in the reaction, and F the Faraday; Eo is the elec-
trode potential of the system when the activities of the oxidant and the
reductant are equal. Polarographic measurements are seldom more
accurate than 1 millivolt, hence substitution of concentrations for
activities will not introduce any appreciable error. Equation (2) may
therefore be written as :
E = E
o
+ nF
RT In [Ox];
[Red];
(3)
E = E 05 = E 0 ' + RT 1 05I
nF n 0.5I
d
d
=
E'
0
(9)
The potential at the point on the polarographic wave where the current
is equal to one-half the diffusion current is termed the half-wave potential
and is designated by E O5 It is quite clear from equation (9) that E O 5
is a characteristic constant for a reversible oxidation-reduction system
and that its value is independent of the concentration of the oxidant
[Ox] in the bulk of the solution. It follows from equations (8) and
(9) that at 25 :
E -- E 05 n
+
0.0591 1 Id - I
og I (10)
K _ [Mn+] [X- bt
(12)
mstab. - [M X~ - Pb)+]
It can be shown * that the expression for the electrode potential can be .
written:
'00591 00591
E O'5 = Eo + -n-
log Kinstab, -
n
-b '{J
- - l o g [X ] . (15)
b
Here p is the coordination number of the complex ion formed, X- is
the complexing agent and n is the number of electrons involved in the
electrode reaction. The concentration of the complex ion does not
enter into equation (15), so that the observed half-wave potential will
be constant and independent of"the concentration of the complex metal
ion. Furthermore, the half-wave potential is more negative the smaller
the value of Kinstab., i.e., the more stable the complex ion. The half-
wave potential will also shift with a change in the concentration of
* Kolthoff and Lingane, Polarography, 1946, p. 163.
Polarography 743
the complex forming agent, and if the former is determined at two
different concentrations of the complex forming agent, we have:
00591 -b
b.EO' 5 = - P . - - - X b. log [X ]
n
This relationship enables one to determine the coordination number p
of the complex ion and thus its formula.
VIII, 3. Quantitative technique.-General considerations. Polaro-
graphic analysis is most conveniently carried out if the concentration
of the electro-active substance is 1O-C lO- 3 molar and the volume of
the solution is between 2 and 25 m!. It is, however, possible to deal
with concentrations as high as 10-2 molar or as low as 10-5 molar and
to employ volumes appreciably less than 1 m!. Under normal condi-
tions (in particular, concentrations of O'OOOl-O'OOlM) and with strict
adherence to established technique, the reproducibility of duplicate
analyses may be as good as 2 per cent.
Oxygen dissolved in electrolytic solutions is easily reduced at the
dropping mercury electrode, and produces a polarogram consisting of
FIG. VIII, 3, 1.
FIG. "'IIJl,5, L
and this fits tightly into a hole drilled in the lower ring, thus ensuring that
the two metal rings can always be returned to the same position relative
to one another. Fig. VIII, 6, 2 will make these devices clear. It maybe
noted that when once the upper mercury reservoir and the lower ring
have been fixed to give a convenient rate of dropping for the particular
capillary in use, the screw holding the support for the mercury reservoir is
tightened with the aid of the special key and all further adjustments (e.g.,
to stop the flow of mercury drops when a determination has been com-
pleted) are made by raising the clamp holding the capillary: in this way
the dropping electrode can always be returned to the original position.
Polarography 75~
FIG. VllI, 6, 4.
,
(e) (f) (g) (h)
(I) (; )
FIG. VIII, 6, 5.
CONSTANT
VOLTAGE
H~' 200/~~~ OLT
- ~~2b'i:LTt+
TRANSFOIltMER
-
ELECTRODES
~J
",,-,
~~I
~3
,,,: .A
=:'~I 'f~oo
t;;~
z_
wo
~< MFD
r
rvvv v
f----'\K\I' .A
I
. A_, v
'f
"i'
A -AA
FIG. VIII, 7, 1.
FIG. VIII, 7, 2.
FIG. VIII, 8, 1.
FIG. VIII, 8, 2.
FIG. VIII, 8, 3.
FIG. Vl lI , 8, 4.
+ !2"A.C:
~s
AMPLIfiER
DROPPING
, MERCURY
ELECTRODE
FIG. VIII, 8, 5.
0-70
0-65
-'
0-60
>=
as
f-
0
"-
0-55
8::;
a.
a.
0-50
-2'5 -2-0 -1-5 -1-0 -0-5 0 0-5 1-0 I-S 200 2-5
lOG. I,;,
FIG. VIII, 9, 1.
be equal to about 0'30, and read off the intercept on the voltage a;:is.
The latter is the half-wave potential for the cadmium ion in N -potas-
sium chloride solution and should be about -064 volt VS. the S.C.E.
VIII. 10. Determination of the half-wave potentials of the zinc and
manganese ions in N-potassium chloride solution.-This determination
is conducted in N-potassium chloride solution as the supporting
electrolyte; the external reference electrode (S.C.E.) is now replaced
by a quiescent mercury pool anode, and the cadmium ion is employed
as a reference ion. The large mercury pool anode is not at a definite
reproducible potential, since the value will depend upon the anions
being discharged upon it; however, by utilising the known half-wave
potential of the cadmium ion (previous Section), the half-wave poten~
tials of the zinc and manganese ions can be readily computed from the
resulting polarogram.
Prepare the following stock solutions :
(a) 1000 g. of Cd++ per litre (from 1856 of anhydrous cadmium
sulphate), 2N-potassium chloride, and 02 per cent gelatin solution (see
previous Section).
(b) 1000 g. of Zn++ per litre (from 24693 g. of anhydrous zinc
sulphate, made by heating A.R. zinc sulphate crystals at 280 0 C.
and cooling in a desiccator). .
(c) 1000 g. ofMn++ per litre (from 27488 g. of anhydrous mangan1"bs
sulphate, made by heating A.R. manganous sulphate at 280 and 0
cooling in a desiccator).
Prepare the test solution by introducing 10 ml. of each of the stock
solutions of cadmium, zinc, and manganese sulphates, 50 ml. of 2N-
potassium chloride solution, and 25 m!. of 02 per cent gelatin solution
into a 100-ml. volumetric flask, and diluting to the mark with distilled
water. The resulting solution contains cadmium, zinc, and manganese
Polarography 765
ions (flach 01 g. per litre) in a base solution of N-potassium chloride and
containing 0005 per cent gelatin solution as suppressor.
Place 2-3 m!. 'If the test solution in an electrolytic cell of the type
depicted in Fig. Vln, 6,5 e (if cells a,j, or i are employed, larger volumes
of the test solution will be required), and remove the dissolved oxygen
by passing nitrogm through the solution for 10-15 minutes. The
electrolysis cell should be immersed in a thermostat at 25 C. Insert
the glass bell carrying the dropping electrode, taking care that the
fine capillary is well immersed in the solution; place 2-3 ml. of water
in the annular space between the bell and the cell so as to form a water-
seal. Stop the passage of nitrogen before commencing the readings.
Adjust the galvanometer sensitivity as before to ensure that the maxi-
mum current will not produce too great a deflection of the galvan-
ometer spot. Then proceed to measure current (galvanometer de-
flection) at gradually increasing negative applied voltages up to about
- 20 volts. Plot the polarogram from the results. Determine the
half-'wave potentials of the three ions from the resulting polarogram;
these occur in the order cadmium, zinc, and manganese with increasing
negative applied potential. Utilising the previously determined value
for the half-wave potential of cadmium ions with reference to the
S.C.E., compute the corresponding figures for zinc and manganous
ions VB. S.C.E. These constants should be of the order of 10 and
15 volts.
VIII, 11. Determination of cadmium in solution.-Two procedures
may be employed: (i) that dependent upon wave height-concentration
plots and (ii) the method of standard additions. The theory has been
given in Section VIII, 4.
(i) Wave height-concentration plots. Prepare from the stock solution
containing 1000 g. Cd++ per litre (Section VIII, 9) solutions containing
respectively 01, 005, 0'025, and 001 g. Cd++ per litre by transferring
to 100-ml. volumetric flasks 10, 5'0, 2'5,* and 1'0* ml. of the stock
solution, adding 50 ml. of 2N -potassium chloride solution and 25 mL
of 02 per cent gelatin solution to each flask and then diluting to the
mark with distilled water. Mix 10 ml. of the unknown solution
(which may contain, say, about 004 g. of cadmium per litre) in a 100-mL
measuring-flask with 50 ml. of 2N -potassium chloride solution and
25 ml. of 02 per cent gelatin solution and dilute to the mark. Record
the polarograms of the four standard solutions and of the unknown
solution following the procedure described in Section VIII, 9, and
determine the wave heights from each polarogram. Draw a calibration
curve (wave heights as ordinates, concentrations as abscissre) for the
four standard solutions: read off from the curve the concentration
corresponding to the wave height of the unknown solution.
(ii) Method of standard additions. The polarogram of the unknown
solution will have been determined under (i). A new polarogram must
now be recorded after the addition of a known volume of a standard .
solution containing the same ion, care being taken that in the resulting
solution the concentration of the supporting electrolyte and the
suppressor are maintained constant.
* More accurate results are obtained by first diluting 10 m!. of the stock solution to
100 m!. in a graduated flask, and then using 25 m!. and 10m!' respectively of the diluted
solution for the preparation of solutions containing 0025 g. and 001 g. of cadmium per
litre.
766 Quantitative Inorganic Analysis
Place 10 ml. of the unknown solution, 5 ml. of the stock solution
(1000 g. Cd/litre), 50 ml. of 2N-potassium chloride solutiorl, and 25
ml. of 02 per cent gelatin solution in a 100-ml. grflduated flask, and
dilute to the mark with distilled water. Transfer a suitable volume to
the electrolytic cell in a thermostat, remove the dissolved air with
nitrogen, and record the polarogram in the usual waf. It is important
that the galvanometer sensitivity be kept at the previous value. Deter-
mine the new wave height x. If y is the wave height obtained with
the unknown solution, the increase in height (x - y) is proportional to
the concentration of cadmium ions added (0'05 g. Cd++ per litre). The
concentration of the unknown solution will therefore be 005 X y/(x-y)
g. of cadmium per litre. Compare this value of the concentration with
that found by method (i).
VIII, 12 .. Investigation of the influence of dissolved oxygen.-The
solubility of oxygen in water at the ordinary laboratory temperature
is about 8 mg. (or 25 X 10-4 mol.) per litre. Oxygen gives two polaro-
graphic waves (0 2 ----"r H 2 0 2 ----"r H 20) which occupy a considerable
voltage range, and their position depends upon the pH of the solution.
Unless the test solution contains a substance which yields a large wave
or waves compared with which those due to oxygen are negl~\ble,
dissolved oxygen will interfere. In general, particularly in dilute
solution, dissolved oxygen must be removed by passing pure nitrogen
or hydrogen through the solution; in alkaline solution the addition of
a little sodium sulphite (01 g. per 10 mI.) is effective.
Place some N-potassium chloride solution containing 0005 per cent
gelatin in an electrolytic cell (for example, Fig. VIII, 6, 5 e, or i)
immersed in a thermostat. Make the usual preliminary adjustments
with regard to sensitivity control of the galvanometer, observe the
current (galvanometer deflection) at increasing values of applied voltage,
and plot the current-applied voltage curve. Now pass oxygen-free
nitrogen through the solution for 10-15 minutes, taking care that the
electrolysis cell is water-sealed. Plot the polarogram using the same
galvanometer sensitivity. It will be observed that the two oxygen
waves are absent in the new polarogram (compare Fig. VIII, 3, I).
VIII, 13. Determination of magnesium with 8-hydroxyquinoline.-
The polarogram of a dilute solution of oxine in 5 per cent ethyl alcohol
consists of two waves, the first with a half-wave potential (E o' 5 ) of
- 139 volts VS. S.C.E., which does not shift appreciably with con-
centration in the range 025-28 X 10-4 mols. per litre, and the second
with a half-wave potential of - 161 volts VS. S.C.E.; the latter shifts
slightly with concentration, and considerably with changes in pH.
The height of the wave at E O' 5 - 139 is proportional-to the concentra-
tion, and is used as the basis of the method for the determination of
magnesium. In effect, the procedure consists in determining the
decrease in wave height of a polarogram of a solution contaiv-ing a
given concentration of oxine due to precipitation of part of the oxine
by magnesium ions in a buffered solution (pH, 10): the removal of the
precipitated magnesium complex is unnecessary, but all elements
which are precipitated by oxine must be absent or be rendered inactive.
Concentrations of magnesium of the order 0'5-5 mg. per litre can be
readily determined with an oxine solution of concentration 05 g. per
litre.
Dissolve 02500 g. of pure magnesium in the minimum volume of
Polarography 767
OOIN-hydrochloric acid and dilute to 250 rol. in a measuring-flask.
Dilute 10 ml. of this solution to 100 ml. in ~L volumetric flask: the
resulting solution will contain 100 mg. of magnesium per litre.
Dissolve 05 g. of A.R. oxine in 50 ml. of rectified spirit and dilute
to 1 litre with water.
Prepare the buffer solution by dissolving 20 g. of A.R. ammonium
chloride in water, adding 10-12 ml. of concentrated ammonia solution
(sp. gr. 0'88) and diluting to 1 litre: adjust to pH 10 by the addition
of a few drops of ammonia and the assistance of pH test strips or a pH
meter. This solution is ca. O25M in total ttmmonia and 004M in
ammonium chloride.
Into each of three IOO-ml. volumetric flasks introduce 20 ml. of the
standard oxine solution, 40 ml. of the buffer solution, and a little
gelatin (02 per cent solution) suppressor. Dilute the first flask to the
mark with distilled water; add 100 ml. (use a micro-burette) of the
standard magnesium solution to the second g,nd dilute to the mark,
thus giving a solution containing 1 mg. of magnesium per litre; add a
suitable volume of the unknown magnesium solution, such that the
final concentration is between 05 and 5 mg. per litre, to the third and
dilute to the mark. Shake the two flasks at intervals during 2 hours;
the magnesium 8-hydroxyq_uinolate will gradually llrecillitate.
Record the polarogram of each solution using a mercury pool anode
and the dropping mercury cathode over the range 0-2 volt in the
usual manner. Determine the wave heights in each case for the first
wave (at ca. 13 volts) after correction for the residual current. With a
knowledge of the decrease in height of the wave produced by the
standard magnesium solution (1 mg. per litre), calculate the magnesium
concentration of the unknown solution from the observed reduction in
height of the wave.
Space does not permit the description of the numerous other deter-
minations for which the polarograph is pl1rticularly suitable, for
example, (a) lead, cadmium, and tin in high-purity zinc and zinc
alloys (8), (b) traces of cobalt in nickel, (2) (c) trl1ces of barium in "pure"
strontium preparations (3), (d) traces of copper, lead, and zinc in pure
aluminium (9), and (e) small amounts of nitfobenzene in aniline (6).
Full details will be found in the selected bibliography given in the
following Section.
768 Quantitative Inorganic Analysis
.
'. 0
l- I-
Z Z
w w
'"'"::::> '"'"::::>
u u
0
I
I End Point
a 0
VOLUME OF REAGENT. J1L. APPLIED VOLTAGE
I-
l- Z
Z w
w
'" '"'"::::>
u'"
::::> u
0
0
I End Point
0 0
VOLUME OF REAGENT, ML. APPLIED VOLTAGE
I-
Z ~.
w w
a<
'"u'"
::::> '":::>
U
.:
, I
0 --- - -----~---------I
End Point
0 0
VOLUME OF REAGENT. ML. APPLIED VOLTAGE
R
@ @
I
I
l-
+ I- I
Z
w
Z
w ____ 1I __ 1I _________
0::
0
!io
0::
.::::> ::>
u I' I
I s
u I I
I I
I I
I
I
I
,
I
I End Point Xl
0 (Anodic) + 0 - (Cathodic)
VOLUME OF REAGENT. ML. APPLIED VOLTAGE
FIG. IX, 1, 1.
~uant~tatwe 1 norgamc Analy8~8
(al (bl
FIG. X, 2, 1. FIG. X, 2, 2.
:'
FIG. X, 6,4.
of these pipettes filled with various absorbents (see Section X, 7), well
corked (or closed by rubber" policemen ") and labelled with the date
on which fresh reagent was introduced. On each occasion that the
pipette is used, the fact is noted on the label; in this way it is possible
to know approximately when it is necessary to re-charge the apparatus.
A pipette suitable for solid (and liquid) reagents, such as phosphorus
in water, is shown in Fig. X, 6, 3. The solid reagent is introduced
through D, which is then closed with a rubber stopper; the latter is
securely wired into place. This pipette is also useful for liquid reagents
\.
786 Quantitative Inorganic AnalY8is
(e.g., potassium hydroxide for carbon dioxide determinations), for it
may be filled with rolls of wire gauze or with fine glass rods before
filling the pipette with the reagent; the gas is thus exposed to a larger
surface of the reagent, and absorption is more rapid.
For solutions which undergo change upon exposure to the air, such
as an alkaline solution of pyrogallol or an ammoniacal solution of
cuprous chloride, the double-absorption pipette (Fig. X, 6, 4) is employed.
E
FIG. X, 6, 5. FIG. X, 6, 0.
FIG. X, 6,7.
J! I
Gas Analysis 787
glass beads or broken glass in order to increase the absorbing surface.
The ends of t~s pipette are closed when not in use by small glass caps,
FIG. X, 6, 8.
upper end of the burette is securely wired. * Open the pinch -clamp at
E, and slip it down over the capillary tube. Pour water that has been
saturated with the gas mixture to be analysed into the burette until
A and B are rather more than half-full. Drive out all the air from the
rubber tubing connecting A and B by raising and lowering the tubes
alternately, keeping the rubber tubing taut during the process. Raise
A until the water begins to flow out of the top of B, then close the
rubber tube of the burette with the pinch-clamp, which is placed close
to the end of the capillary. Compress the rubber tubing at C between
the thumb and fingers of the left hand, and pour out the excess of water
that is in A.
The next step is to measure out exactly 100 ml. of the gas sample. Insert
into the rubber tube at E a capillary tube connected with the supply
of the gas to be analysed, after first displacing the air in this connecting
capillary by the gas. Hold the upper part of A in the left hand, lower
it below B, and open the pinch-clamp E with the right hand. Intro-
duce somewhat more than 100 ml. of gas into the burette. Close the
pinch-cock E, level A and B, and allow the water in the burette to drain
for 2 minutes. Disconnect the capillary tube from the source of gas,
and adjust the volume of the gas by suitably manipulating the pinch-
clamp until it is exactly 100 mI., when the levels of the liquids in the
two tubes are the same.
The next stage is the absorption of one of the gaseous compone1J,ts of
the mixture. Connect the burette and absorptio~ pipette exactly as in
Fig. X, 6, 9: the burette and levelling tube should be on a flat table.
Insert into the rubber tubing G the bent capillary tube F. This con-
necting capillary has the same dimensions as the capillary tubes of the
burette and pipette, viz., 6 mm. external and 1 mm. internal diameter;
the horizontal portion is about 6 cm. long and the legs each about 2.5
cm. long. Slip a long piece of rubber tubing over the tube H of the
pipette. Grasp F between the thumb and fingers of the right hand,
squeeze the rubber tube E on the capillary tube of the burette between
the thumb and fingers of the left hand, blow gently through H until the
liquid in the pipette is driven over to a mark on the farther end of the
horizontal portion of the capillary tube F, and then insert the end of
F into the rubber tube on the burette. If the connexion is properly
made, there will be practically no movement of the reagent in the
capillary. Even if the air enclosed in the connexion between the burette
and pipette should occupy about 1 cm. length of the capillary, the error
may be neglected, since capillary tubing of about 1 mm. bore occupies
only about 001 ml. per cm. length. If, however, more than 1 cm.
length of air remains in F, F should be slipped out of E and the opera-
tion repeated. t The apparatus is now ready for the absorption of a gas.
* \Vhen joining together glass tubes by rubber tubing, the ends of the tubes should
be rounded off in the flame, and then brought close together within the piece of rubber
tubing. The rubber tubing is secured in place by means of wire ligatures, composed of
copper wire about 1-2 mm. in diameter. Each ligature should consist of only one turn
of the wire around the tube, the ends being drawn and tightly twisted together by means
of a pair of pliers. Long rubber connexions should be avoided, not only because the
rubber tubing is somewhat porous, but also because air in the tube tends to adhere
tenaciously to the walls.
t Certain reagents must never be allowed to come into contact with the rubber
connexion at G; in such cases, the liquid from the pipette is forced upwards until it
stands just below this rubber connexion and allowance is made for the air remaining
in the capillary tubes. The correction is readily made, since 10 cm. of the lmm.-bore
capillary corresponds to ca. 01 m!. of air.
(jas Analysis 789
Open the pinch-clamp E, and slowly raise the levelling-tube A, thus
driving the gas over into the pipette. Allow the water to flow into
the capillary tube F until it reaches the point to which the reagent has
been driven over, and then close the pinch-clamp. A thin layer of the
reagent adheres to the walls of the capillary, and this is sufficient to
remove most of the absorbable constituent of the gas mixture remaining
in the capillary. With some gases (e.g., carbon dioxide) absorption
occurs rapidly in the pipette, but with others (e.g., oxygen and carbon
monoxide) it is necessary to shake the pipette after the gas has been
transferred into it. In the latter case, place another pinch-clamp on
G, holdthe burette in the left hand and gently rock the pipette stand
backward and forward on the front edge of the base. After the con-
stituent that is to be removed is completely absorbed, the gas is trans-
ferred back into the burette. This is done by holding the levelling-
tube in the left hand and in such a position that the confining liquid in
it stands at a slightly lower level than in the burette, open pinch-clamp
E (and, if necessary, that at G)
and lower the levelling-tube
slowly until the gas is drawn
back into the burette and the
liquid in the pipette reaches a
point on F at which it origi-
nally stood; close the pinch-
clamp E, level approximately,
allow the water to drain for
2 minutes, level accurately,
and take the reading of the
volume of the gas in the
burette. Absorption may not
be complete in one operation. FIG. X, 6, 10.
It is therefore advisable to
transfer the gas back to the absorption pipette and to repeat the
process until no further diminution in volume occurs.
By the use of a series of Hempel pipettes the gas is subjected to the
action of various absorbents, one after another, until the complete
composition is ascertained. As already pointed out, the connexions
must in all cases be made with stout rubber tubing (" pressure"
tubing) which are secured with copper-wire ligatures.
For gases which are appreciably soluble in water, the levelling-tube
containing water cannot, of course, be used. The clean burette, which
must be of the Hempel-Winckler type, is first thoroughly dried by
washing it successively with alcohol and ether (alternatively by acetone
. alone) and then drawing air through it. The dry burette is filled with
the gas either by the pressure of the gas or by using an aspirator bottle
attached to the three-way tap to draw out the air and replace it with
the gas; when the burette is full, the taps are turned off, care being
taken that the gas is at atmospheric pressure. Connexion may then
be made with the levelling-tube A, which is then filled with water, the
lower tap opened so that the water flows into the burette and absorbs
the soluble gases present. As the burette holds exactly 100 ml.
between the three-way tap and the upper tap, the percentage of soluble
gas can be read off directly.
The manipulation of the Hempel apparatus may be considerably
790 (Juantitative inorganic Analy8~8
(a) (b)
FIG. X, 6, 11.
close the tap. Dip the end of the burette into a dish containing water,
which then rises in the tube. Close tap B, open tap A so that water
flows into the burette from the cup 0 until the original pressure is
produced. Add more water until it stands at the upper mark in the
cup, and open tap A cautiously to reproduce the original pressure.
Read the volume of the residual gas: the difference in volume gives
the concentration directly in percentage by volume of 'the constituent
absorbed.
The Bunte burette may be employed inter alia for the determination
of carbon dioxide (by aqueous potassium hydroxide ), heavy hydrocarbons
(by bromine water), oxygen (by an alkaline solution of pyrogallol or,
better, by alkaline sodium hyposulphite solution), and carbon monoxide
(by ammoniacal cuprous chloride solution).
C. Orsat's apparatus. This apparatus, introduced by Orsat in 1874
and since modified by numerous workers, is widely used where an
accuracy of about 05 per cent suffices, e.r/, for furnace-gas analysis.
The method of analysis is essentially similar to that with the Hempel
apparatus, but the burette, pipettes, and accessories are so designed
that the whole apparatus, including three or four absorption pipettes,
fits into a portable box.
The Orsat-Lunge apparatus is shown in Fig. X, 6, 12. It consists of
a water-jacketed burette of 100 ml. capacity, attached by means of a
capillary tube manifold to four pipettes, three of which contain absor-
bents for carbon dioxide, oxygen, and carbon monoxide respectively,
and which are usually filled with glass tubes or rods to present a greater
surface of the reagent to the gas; the fourth pipette contains water
only and is used in conjunction with a tube containing purified asbestos
impregnated with palladium and heated by means of a small spirit
lamp. The last pipette and palladium-asbestos tube are omitted in
some forms of the apparatus. The burette and reservoir to which it is
attached contain acidulated water coloured with a suitable indicator,
so that an indication is given at once of any accidental fouling with
reagents. The gas mixture is drawn into the apparatus through the
filter shown on the outside of the case (the filter may be dispensed with
when working with gases free from dust) and through the three-way
stopcock. If the gas to be sampled is at less than atmospheric pressure,
the sampling tubes and filter are filled with gas by operation of a rubber
aspirator (not shown in the figure) before the stopcock is connected
with the measuring-burette. The first sample of gas drawn into the
burette is discarded, it being employed to expel the air from the
capillary connecting tubes. The reagent in each pipette is adjusted
to a standard line just below the rubber connexion, and in no cir-
cumstances must any of the reagent be drawn above the tap.
The method of carrying out the absorptions for carbon dioxide,
oxygen, and carbon monoxide is obvious (it is similar to that employed
with the Hempel apparatus), and need not be further described. For
the determination of hydrogen, which must be carried out after the
above gases have been removed from the gaseous mixture, air is allowed
to enter the burette until the total volume is approximately 100 ml.
and the exact volume is read. The small capillary containing pall:;t-
dinised asbestos (situated at the left of the bulb containing water) is
gently heated by means of a small spirit lamp, and the gas is passed
very slowly from the burette into the pipette: the hydrogen will com-
(Jas Analysis 7U3
bine with the oxygen at the surface of the catalyst. The gas is returned
to the burette and the process repeated, after which the volume of the
residual gas is measured. Two-thirds of the contraction represents
the volume of hydrogen. If the temperature is not allowed to rise
above 200 C., the volume of any methane and its homologues present
FIG. X, 6, 12.
--~
yuantnatwe lnorgamc Analy8~8
THERMOMnER
MANOMETER
M
"
FIG. X, 6, 14-.
FIG. X, 6, 15.
~(Fig. X, 6, 15) at levels near the top and bottom of the manometer
scale.
The general mode of use of the apparatus is as follows:
1. Introduce the gas sample (up to 10 ml.) into the vessel B by means
of the capillary tube H, the tap T 1 and the reservoir R 2
2. Reverse the tap Tv and transfer the gas to the measuring-vessel
A. Run the mercury to the mark K, and thus seal the gas in the
burette.
3. Introduce a quantity of the appropriate absorbent into B from
H by suitably manipulating T 1 and R 2
4. Transfer the gas to B with the aid of 111 and T 2 Absorption will
take place.
5. Transfer the residual gas back into the measuring-burette A by-
raising R2 and suitably turning T 1 As soon as the absorbent liquid
has reached the left-hand side of the tap T 1> reverse the latter, and
drive out the reagent through H. Then reverse the tap, and adjust
the mercury to the mark K as before.
The method of measurement of the gas varies according as to whether
precision results (within 01 per cent) or moderately accurate (" techni-
cal," i.e., within 05 per cent) are required. The measuring-vessel
consists of a burette of 10 ml. capacity, clllibrated in 01 ml. Below
the lO-ml. mark the burette narrows to a bore of 3 mm., and a mark F
(jas Analysis 797
is etched round the lower part. Either varying volumes or varying
pressures may be measured; the temperature is assumed constant,
but may be corrected for if variations occur. The constant-volume
method is the more accurate. Three procedures will be described.
(a) Vctrying volume and constant pressure. This is the quickest
procedure and yields results of "technical" accuracy. Level the
mercury in the burette with the mercury in Rv which is held in the
hand, and read the volume.
(b) Varying volume and approximately constant pressure (corrected).
This modification of the constant pressure method is the most satis-
factory for precision work. Bring the gas in the burette to approxi-
mately atmospheric pressure (say, to within 2 mm.), close the tap T 2 ,
and read both the burette and manometer. The pressure in the burette
is the~ equal to the atmospheric pressure, plus the difference between
the manometer reading and the reading of the manometer when the
burette is filled to the same mark at atmospheric pressure. Let us call
this difference !:lP.
The manometer readings corresponding with the different burette
readings at atmospheric pressure are a constant of the apparatus, and
are determined once and for all by measuring a few points with the
tap T 1 removed. These are plotted in the form of a graph, which is a
straight line.
The correction to the burette reading is applied as follows. Let P
be the atmospheric pressure, p the vapour pressure of water, V the
burette reading (i.e., the volume of moist gas at the experimental
pressure), and Va what the burette reading would have been if the
mercury had been levelled to exactly atmospheric pressure. Then:
V a-- V X P - P +!:lP
---.p~--
-p
!:lP
or Va,-V=VX p- -
-p
If !:lP is not greater than 1 cm., then any deviation of P - p from the
average approximate figure (76 - 1) = 75 cm. will not affect the cor-
rection sufficiently to introduce an error of more than 01 per cent on
the total gas. In practice, !:lP does not exceed 2 mm.; the magnitude
of the correction, for 1 mm. of !:lP, is:
V X (01/75) = V X 00013, i.e., 013 per cent of V
(c) Varying pressure and constant volume. Many gas samples which
. occur in practice do not involve contractions greater than about 30
per cent of the total gas; for this purpose a manometer of 30 cm. length
will suffice. In such cases the maximum accuracy is obtained by the
constant-volume method. A knowledge of the volume is not required,
and the result will be independent of any errors in the graduation of
the burette. The mark F serves as a levelling-mark for this purpose,
and the bulb below the water-jacket enables a sufficient volume of gas
to be taken in the measuring-burette at atmospheric pressure to be
compressed to ca. 105 ml. (volume to mark F) at about 100 cm.pressure.
It can be shown that the volume of the gas (at normal pressure)
contained in the burette is proportional to :
P +A -K -p/76
798 Quantitative Inorganic Analysi8
where A is the manometer reading and K is the manometer reading
with the burette at atmospheric pressure {a.U pressures are expressed
in cm. of mercury).
Any other graduation may, of course, be employed, as in the case of
samples which are not large enough to fill the burette. The precision
then is somewhat less, since any error in levelling in the wider tube
causes a greater error in volume.
Mention must be made of the fact that the vessel B may be fitted
either with a spark gap or with a platinum spiral for the burning of
hydrogen and other combustible gases; the platinum spiral is of
greater general utility. Gas mixtures containing more than 10 per
cent of hydrogen or 3 per cent of hydrocarbons Ehould be diluted with
air before combustion.
The apparatus is applicable to all gases commonly dealt wiih. It
can be used equally well for precise general analysis and for rapid
technical analysis, and the volume of the sample required is small
(normally 10 mI.). The use of mercury as the confining liquid increases
the speed of transference of the gas, and determinations are corre-
spondingly rapid.
E. Bone and Wheeler apparatus. This, in its simple or one of its
modified forms, is probably the
most widely used instrument for
~xact analysis in Great Britain,
and is applicable to most classes
of gaseous mixtures. The usual
form of Bone-Wheeler apparatus is
shown in Fig. X, 6,16. The gas
mixture is measured at constant
volume in limb A of the water- .
jacketed U-tube, the pressure
being measured by the height of
the mercury column in the limb
B, which is graduated upwards
in millimetres. The limb A has
a series of graduations coincid-
ing in level with each integral
100-mm. mark on B. The
heights of A and B are such, that
when a measurement is being
made, the closed space above the
mercury in' B is a Torricellian
vacuum except for water vapour; .
both limbs are kept saturated
with water by means of a small'
quantity of dilute sulphuric acid
(2-5 per cent). The pressure of
the gas in A is equal to the differ-
ence in the level of the mercury
in Band A. Variations in the
FIG. X, 6, 16.
atmospheric pressure during the
analysis do not affect the results,
but variations in temperature do affect the readings, and corrections
must be calculated (see Section X, 4). Mercury is raised or lowered by
Gas Analysis 799
means of the reservoir D, which is connected to a windlass and'ratchet;
fine adjustment in levelling on to the marks is obtained by means of
a special tap C, which separates the limbs A and B from D.
FIG. X, 6, 17.
Na 2S 20 4 +O +H 0
2 2 = N&HS0 4 + NaHSO a
A suitable solution for general use is prepared by dissolving 50 g. of
commercial sodium hyposulphite in 250 ml. of water, 30 g. of sodium
hydroxide in 40 ml. of water, and mixiog the solutions. * One ml. of
this solution will absorb 105 ml. of oxygen. The absorption of oxygen
is slower than with alkaline pyrogallol, but absorption also takes place at
low temperatures at which the latter reagent is ineffective. Further-
more, no carbon monoxide is evolved or absorbed, and the reagent is
unaffected by unsaturated hydrocarbons.
The rate of absorption can be considerably increased by the addition
of sodium anthraquinone-f3-trnlphonate. Fieser (1924) recommends a
solution of 16 g. of sodium hyposulphite, 66 g. of sodium..hydroxide,
2 g. of sodium anthraquinone-f3-sulphonate, and 100 ml. of water.
When this solution is exhausted, its colour changes from blood-red to
brown; vigorous shaking is unnecessary. The reagent should not be
kept for more than one week. '.
Solid phosphorus. Yellow phosphorus in the form of thin sticks may
be employed for the absorption of oxygen in the Hempel pipette for
solid reagents (Fig. X, 6, 3) and in Orsat pipettes. A great advantage
is that once a pipette has been charged with the reagent, it does not
require renewing except after long periods. Absorption generally
takes about 3 minutes: the oxygen content of the gas should not
exceed 50 per cent., otherwise explosions may occur. During the
absorption white clouds of oxide are produced and dissolve
in the water: the clearing of these is a sign that absorption is
complete. The water in which the phosphorus is immersed should be
changed from time to time in order to remove the phosphoric and
phosphorous acids which are formed. The phosphorus should be
shielded from light, otherwise a layer of red phosphorus will be formed
on the surface. The temperature should be above 15 C.-below this
temperature absorption is extremely sloW. Even small quantities of
* For use in the Bunte burette, a solution of 10 g. of Na 2 S 2 0. in 50 m!. of water
mixed with 50 m!. of 10 per cent sodium hydroxide solution is preferable.
Gas Analysis 803
acetylene and unsaturated hydrocarbons must be absent, for these
inhibit the reaction.
D. Oarbon monoxide. The usual reagent for the absorption of
carbon monoxide is ammoniacal cuprous chloride solution, which forms a
complex CuCl,2H 2 0,CO. The reagent may be prepared for use in the
Ambler or Bone-Wheeler type of apparatus by adding 75 g. of white
cuprous chloride to a solution of 15 g. of ammonium chloride in 80 mL
of water, and then adding sufficient concentrated ammonia solution
until solution is complete. The solution should be kept in contact
with copper wire or turnings in a stoppered bottle. For use in Hempel
pipettes or in the Orsat type of apparatus, 125 ml. of concentrated
hydrochloric acid are added to 40 g. of cuprous chloride in a suitable
flask, followed by the cautious addition of 130 mL of concentrated
ammonia solution, the flask being cooled to atmospheric temperature:
a little more ammonia solution (ca. 15 ml.) is then introduced until the
white precipitate just dissolves.
The absorption of carbon monoxide by either of the above solutions
is slow, and intimate contact between the gas and liquid is necessary.
If the gaseous mixture contains more than 10 per cent of carbon mon-
oxide, it should be treated a second time with a fresh solution. After
the absorption ammonia must be removed from the gas by washing
with water or with dilute sulphuric acid. Oxygen, acetylene, and to
some extent, olefines are absorbed by the reagent, and must
previously be removed as already described.
A better reagent is cuprous sulphate-fi-naphthol, with which a stable
compound Cu 2SO 4,2CO is formed. The reagent is prepared by cautiously
adding 200 mL of concentrated sulphuric acid, specific gravity 184,
to 25 ml. of water; the cool solution is added a little at a time to 20 g.
of specially prepared cuprous oxide contained in a mortar, and the
mixture is well ground to obtain the solid in fine suspension. 25 Grams
of pure fi-naphthol is added and incorporated in the mixture by grind-
ing; the final mixture is filtered through glass wool or through a
sintered-glass funnel, and at once transferred to the absorption pipette.
The reagent must be maintained above 15 C. and protected from the
atmosphere; the fi-naphthol separates out at a lower temperature, and
the mixture slowly oxidises if exposed to the atmosphere.
The cuprous oxide is prepared as follows. 100 Grams of cupric acetate are
added to 1 litre of distilled water contained in a 2-litre flask, and the mixture
heated until the acetate is dissolved. The solution is filtered, heated to the
boiling point, treated with a solution of 60 g. of glucose in 400 ml. of water,
the boiling continued until the blue colour fades somewhat, and the mixture
allowed to stand until the red cuprous oxide separates out. The cuprous
oxide is washed several times with water by decantation, transferred to a
filter, washed once with alcohol, and finally dried in a vacuum desiccator.
The cuprous sulphate-fi-naphthol reagent absorbs carbon monoxide
completely (1 mI. absorbs ca. 5 mI. of CO), but not hydrogen or methane;
it is, however, rather slow in action, and absorption may take up to
30 minutes. The gas should be washed with potassium hydroxide
solution after contact with the reagent, since traces of acid fumes are
liable to be produced. '
E. Hydrogen. Hydrogen is usually determined, together with
methane, etc., by combustion (Section X, 8). However, in some cases
it may be desirable to determine the gas by absorption.
804 Quantitative Inorganic Analysis
The chief absorbent is palladium. If hydrogen IS brought into
contact with palladium in the presence of oxygen, the hydrogen is
removed partly by absorption and partly by catalytic combustion.
Two-thirds of the contraction is equal to the volume of hydrogen
present. The method is far from accurate, since any carbon monoxide
and methane present may be partly oxidised too. If palladinised
asbestos at 100 C. is used, for example, in the Orsat apparatus (Section
X, 6C), the percentage of carbon monoxide and methane burnt will be
small, and an approximate value for the hydrogen content may be
obtained; in technical analysis this value is corrected by determining
the carbon dioxide simultaneously produced and adding this value to
the initial contraction observed-a procedure which is open to many
objections. The most satisfactory results are obtainable with a
fractional-combustion" pipette" (see Section X, 6C).
X, 8. Determination by explosion and combustion methods.-The
most important gases determined by combustion methods are hydro-
gen, carbon monoxide, and saturated hydrocarbons (methane CH 4 ,
ethane C2H s ' etc.). The combustion of these gases with\ excess of
oxygen supplies three results, from which it is possible to determine
the amount of gas burned and, in simple cases, its identity. The
observations which can be made are:
(i) Contraction in volume, VI.
(ii) Volume of carbon dioxide produced, V 2 (determined by
absorption in alkali after the combustion).
(iii) Volume of oxygen consumed, V3 (determined by absorption
after the removal oBhe carbon dioxide).
In the following table the volume changes for a number of simple
gases are shown; these refer to one volume of the combustible gas.
~'l
I t'2 1- ~'3
The various equations from which the above table is derived are
obvious, and include the following/or the commonly encountered gases:
2H2 + O2 __:_ 2H 0 2
2CO + O2 = 2C0 2
CH 4+ 20 2 . CO + 2H 20
2
\(
Q '" ~
T, roM. , ..
mercury reservOir
}<'w. X, 8, 1. FIG. X, 8, 2.
I
CHAPTER XI
MICRO-GRAVIMETRIC AND MICRO-VOLUMETRIC ANALYSIS
XI, 1. General Discussion.-Macro-gravimetric analysis usually
involves the accurate weighing of 01-05 g. of material, and macro-
volumetric analysis is concerned with the precise measurement of 10-
50 ml. of reagent. To secure the same order of accuracy in the final
result when working with smaller quantities of materials, say of the
order of one-tenth or one-hundredth of the above quantities, the mere
scaling down of existing macro-chemical techniques described in
Chapters III and IV is not always satisfactory. Special techniques
have been developed for small-scale analysis which yield results of the
same order of accuracy as those obtainable by macro methods: it is
the purpose of the present chapter to provide a short introduction to
the subject.
In the first place the terms semi-micro-analysis and micro-analysis
require some explanation. Semi-micro-analysis is concerned with the
manipulation of 10-100 mg. of material, whilst micro-analysis deals
with 1-10 mg. of material; semi-micro-analysis has been termed
centigram analysis, and wicro-analysis is sometimes called milligram
analysis. There is clearly no sharp line of demarcation between the
two, although the broad significance of the two terms is now well
established. In practice, semi-micro-analysis is generally carried out
with the aid of a balance sensitive to 001 mg., whilst for micro-analysis
a balance sensitive to 0001 mg. (ly) is employed. Most of the appara-
tus required for semi-micro-analysis is available commercially and,
apart from the balance, is comparatively inexpensive. This apparatus
will be described below; much of it can be employed for micro-analysis
by obvious modifications of the technique, once that for semi-micro-
analysis has been mastered. The training of large classes of students
in micro-methods is, under the normal conditions existing in the average
college or university laboratory, more conveniently carried out by experi-
ments on the semi-micro-scale; the essential differences between macro-
and micro-techniques will thus be appreciated and the broad features
of the new techniques acquired. If the facilities are available (micro-
balances reading to 0001 mg., etc.), micro-analysis (milligram analysis)
should be carried out.
XI, 2. Micro-balances.-A typical semimicro-balance, sensitive to
001 mg., has been described in Section II, 9F. A micro-balance
(Oertling, No. 63. PAjPB), maximum load 20 g. and direct reading to
0001 mg. (1 microgram = 1y), is illustrated in Fig. XI, 2, 1. The
beam, which carries a 5-mg. rider, is serrated into 100 parts: movement
of the rider along the beam from one notch to the next represents a
difference in weight of 01 mg. The pointer carries a tiny, finely
divided graticule (200 divisions), and a magnified reflection of this is
shown on an illuminated ground -glass screen at the top of the balance
case; 01 mg. swings the pointer approximately 100 divisions, thus
enabling readings to be made to 0001 mg.
814
Micro-gravimetric a7}d Micro-volumetric Analysis 815
It will be evident that for accurate weighings to 1 microgram, the
balance must be properly sited. The following points must be taken
into consideration when setting up a micro-balance.
1. The balance should preferably be located in a separate room and
be supported upon a stone slab mounted upon supports about 2 ft.
6 in. high. The latter should, if possible, be of stone or brick and not
be connected with the walls of the balance room. Ideally, the supports
FIG. X I , 2, 1.
(a) (b)
FIG. XI, 3, l.
c-
=0=0000000
I 1
:=IO~OOCOC~O
2>1
(u) (b)
FIG. XI, 3, 3.
pressure should be dried with the same drying agent. Since the sample
is small, drying is, as a rule, quickly accomplished under reduced
pressure. For substances which must be dried at higher temperatures
but at normal pressure, a thermostatically controlled electric drying
oven may be used.
Drying under reduced pressure in a current of dry air, either at the
laboratory temperature or more usually at higher temperatures, may
be carried out rapidly and efficiently by means of the Pregl micro-
desiccator illustrated in Fig. Xl, 3, 4. It consists of a glass tube 24-
+-------
TO PUMP
. FIG. XI, 3, 4.
FIG. XI, 3, 5.
on the bench) serve to hold the drying tube T in position in the drying
block; F is charged with anhydrous calcium chloride, held in position
between plugs of glass or cotton wool, to dry the air entering the
apparatus. The experimental details for drying a filter-stick (Section
XI, 4A) and its associated beaker will now be given.
The drying block is heated to the required temperature and the
burner is regulated so that this temperature is maintained. The guard
tube F is removed and the tube S is pushed into the drying tube T
until the end N projects beyond the tube. Without being removed
from the micro-beaker, the filter-stick is connected to the end N by a
short length of rubber valve tubing; the tube S is now drawn back
into the drying tube T, care being taken that the micro-beaker follows
the movement of the filter-stick. As soon as the open end of the micro-
beaker is inside the drying tube T, the operation may be completed by
holding the drying tube vertically whilst pulling S back into the tube.
The final position of the micro-beaker and filter-stick is as shown in the
figure: the rubber connexion at N is outside the heated part of the
tube and an air-tight seal is formed at M. The guard tube F is now
placed in position and tube S is connected to a pump. The drying
tube is placed in the drying block B, and the two corks C are pressed
tightly towards the side of the block. The stream of dry, filtered air
enters at F and passes through the micro-beaker and filter-stick as
indicated by the arrows in the diagram. When drying is complete,
the drying tube T is taken out of the drying block without interrupting
the suction and placed upon a sheet of clean paper. The guard tube F
is removed and the micro-beaker is transferred to the paper by pushing
the narrow-bore tube S into the tube T: the filter-stick, whilst being
820 Quantitative Inorganic Analysis
retained in the micro-beaker, is disconnected at N. The pump is now
turned off, the tube S is drawn back so as to form an air-tight seal at
M, and the guard tube F is inserted in order to prevent dust from enter-
ing the drying chamber T. The end of the filter-stick which was con-
nected to N is carefully cleaned with a linen cloth and, whilst retaining
the filter-stick in the beaker, the outside of the beaker is wiped with
a moist and then with a dry chamois leather as detailed in Section XI, 2.
The beaker and filter-stick are then placed in a desiccator (e.g., Fig.
XI, 3, 2). After leaving near the balance case for 10 minutes, the
beaker is transferred to the balance pan by means of forceps (Fig.
XI, 4, 3a); if the frame (Fig. XI, 4, 2b) is used, the filter-stick may
remain in the beaker. It is recommended that the tare consist of a
beaker of similar size and that rods of soft glass (4 mm. and 1 mm.
diameter, cleaned with moist and dry chamois leather) held by means
of a piece of chamois leather or with forceps be added until the total
weight of the tare is slightly less than that of the beaker and filter-stick;
the difference in weight should preferably be about 05 gm. for micro-
analysis, but may be appreciably more for semimicro work. Finally,
the doors of the balance are opened and the weighing is performed after
10 minutes. If it is desired to check the constancy in weight of the
beaker and filter-stick, the beaker is filled with distilled water, the
water is drawn off through the filter-stick, and the drying and weighing
procedures are repeated.
C. Beakers. The following beakers are available commercially:
Pyrex, low f<,lrm with pour-out lip, 5, 10, 15, 20, and 30 ml.; Pyrex,
round bottom, 5 and 10 ml.; Hysil, with or without lip, 1, 5, 10, 15,
and 20 ml.
D. Flasks. The following flasks may be purchased: Pyrex, round-
bottomed, 5, 10, and 25 ml.; Hysil, round-bottomed, 5, 10, 15, 20,
25, and 30 ml.; Pyrex or Hysil conical (Erlenmeyer) flasks, 5, 10, 15,
and 25 ml.; Pyrex or Hyeil filter-flasks with side tube, 25, 50, and 125 ml. "
E. Evaporating basins or dishes. The following evaporating basins
are suitable for micro-chemical analysis: deep form with lip, Royal
Worcester, 13 ml., Coors porcelain, 10, 22, and 35 mI.; flat form with
lip, Royal Worcester, 10 and 25 ml.
F. Crucibles. Micro-crucibles of approximate capacities 1, :1, G, 8,
11, and 15 ml. in porcelain and in platinum may be purchased.
Micro-crucibles for the collection of precipitates have been designed
by Nebauer: the original type was 14 mm. high, 12 mm. wide at the
top, and 10 mm. at the base. Such crucibles, when -made of platinum,
have a filtering-rod of compressed platinum-iridium sponge; when in
porcelain, the base is of unglazed niaterial. Each crucible is provided
with a lid and also with a small capsule to cover the base; it should not
be weighed without both of these. The dimensions have been modified,
but the name Nebauer crucible has been retained. Micro-filter-crucibles,
with saucer (capsule) and lid, provided with porous bottoms are
standard commercial products: Royal Worcester, 1 ml. (height 15
mm., diameter at bottom 12 mm., diameter at top 15 mm.) and 3 m!.
(22 X 14 X 10 mm.); Selas micro, 12 ml. (height 16 mm., diameter at
bottom 12 mm.) and 26 ml. (23 X 12 mm.); Selas semi-micro, 55 m!.
(31 X 16 mm.) and 7 ml. (37 X 16 mm.).
G. Burners. The diminutive form of the Bunsen burner, the so-
called arsenic burner, is useful in semi-micro-work. Micro-burners of
Micro-gravimetric and Micro-volumetric Analysis 821
excellent design are marketed by most dealers and/or manufacturers
of scientific apparatus.
H. Water-baths. Micro-beakers and similar glass apparatus are
never heated directly with a flame. The device (a) (Fig. XI, 3, 6) may
...........1 ,
... _
o
(a) (b)
FIG. XI, 3, 6.
be used for beakers; the metal ring rests on top of the beaker in which
water is boiled. The device (b) is shown inside the associated 250-ml.
Pyrex conical flask. The deep indentations, symmetrically placed,
serve to support the micro-vessel.
I. Drying blocks. For drying substances, crucibles, etc., at tem-
peratures of 100-200 C. at atmospheric pressure, the drying block
shown in Fig. XI, 3, 7 may be employed. The solid metal block is
FIG. Xl, 3, 7.
(a)
(b)
.c~.==~_~)
(c)
c:=J~===================
(d)
\
~ ~~========~
(e)
(f)
FIG. XI, 3, 8.
ternal ground-glass cap. Types (d) and (e) are long-handled weighing-
tubes (tube, 20 X 5 mm.; handle, 10 cm. long); these are useful for
weighing out a solid substance which is afterwards transferred to another
vessel, such as a conical flask. Type (f) is a micro weighing-bottle
(" weighing piggy"); it is generally employed for weighing out hygro-
scopic substances in a platinum or porcelain boat.
Micro-gravimetric and Micro-volumetric Analysis 823
K. Centrifuges, Centrifuges are generally employed to separate a
suspended solid from a liquid. An electrically-driven centrifuge,
capable of giving speeds up to 3,000 revolutions per minute, is recom-
mended for quantitative analysis. A full discussion of the theory and
also of the applications of the centrifuge to qualitative inorganic analysis
has been given elsewhere * by the author. It may, however, be
desirable to discuss here the general precautions to be taken in the use
of the centrifuge. These include:
1. The masses at the centrifuge head must always be balanced (to
within 01 g.) before starting the centrifuge.
2. Centrifuge tubes should not be filled to more than 25 cm. from the
rims of the tubes.
3. The cover must be placed on the shield before starting and it
must not be removed before the centrifuge has come to rest.
4. All electrically-driven centrifuges are fitted with variable resis-
tances. They should be started off at low speeds of rotation and
gradually raised to the maximum required as indicated upon the
revolution counter. At the end of the appropriate period the speed
of rotation must be reduced gradually, since violent changes of speed
of revolution tend to disturb the precipitate.
5. The liquid may be separated from the solid by decantation.
The tube is inverted gradually and the liquid allowed to flow out at
moderate speed, and the angle of inversion is maintained consistent
with the volume of liquid remaining in the tube. The centrifuge tube
is then inverted over a pad of filter paper and the residual liquid
permitted to drain from the walls of the tube. Any liquid adhering
to the rim of the tube is removed with filter paper. Alternatively,
the mother liquor may be removed with the aid of a dropper
pipette.
6. The precipitate must usually be purified by washing. This may
be done by holding the centrifuge tube loosely in one hand and gently
tapping the bottom of the tube with the fingers of the other hand so as
to splash the precipitate up the sides of the tube. A known volume
of wash liquid is then added from a calibrated pipette, care being
taken that the sides of the tube are washed thoroughly. The bottom
of the tube is flicked gently with the fingers to ensure intimate contact
between the precipitate and the wash-liquor. The suspension is then
centrifuged again. It is usually considered necessary to repeat the
washing and centrifuging twice for the complete removal of the excess
of the original precipitating reagent.
XI, 4. Apparatus for quantitative fiItration.-The most widely used
method for quantitative filtration in gravimetric analysis utilises
the filter-stick. Micro filter-beakers, filter-tubes, and crucibles also
find application for the same purpose. A description of all of these
follows.
A. Filter sticks. In any attempt to reduce the scale of macrogravi-
metric determinations, a major source of error lies in the transference
of precipitates from the beaker (or precipitation vessel) to the filter.
The error may be eliminated altogether by the use of a filter-stick, first
developed by F. Emich. The filter-stick is used for upward filtration
* A. 1. Vogel, A Text Book of Qualitative Ohemical Analysis including Semimicro
Qualitative AnalY8is. Third Ed.ition, 1945, pp. 487-492 (Longrnans, Green and Co.,
Ltd.).
824 Quantitative Inorganic Analysis
in a manner which will become evident upon inspection of Fig. XI, 4,
I. A filter-stick is always associated with a particular beaker or
...
(a) (b)
FIG. XI, 4, 1.
crucible; they are kept together in a special little rack and weighed
together before and after the determination.
Pyrex round-bottomed beakers of 5 and 10 ml. capacity are marketed;
they are usually supported in a metal stand (Fig. XI, 4, 2, a). The
(a) (b)
FIG. XI, 4, 2.
Fm. -,YE, d, 3.
disc. Porcelain filter-sticks have a porous disc fused at the lower end:
in the Royal Worcester micro-filter-stick the porous plate has a
diameter of 10 mm. and the tube is 50 mm. long. The Selas Corpora-
tion market a micro-filter-stick (9 X 57 mm.) and a semimicro-filter-
stick (20 X 85 mm.).
Before use, the filter-stick and associated beaker (or crucible) are
cleaned by filling the beaker with chromic acid mixture or with con-
centrated nitric acid, inserting the filter-stick into the beaker and
heating on a water-bath. After about 10 minutes most of the acid is
removed from the beaker by means of a pipette fitted with a rubber
teat, and the beaker is filled with water. The diluted acid is removed
by suction through the filter-stick; the beaker is filled several times
with distilled water, and is similarly emptied by suction. The filter-
stick and beaker are now dried, preferably in a Benedetti-Pichler drier
(Fig. XI, 3, 5) at the same temperature as will be used subsequently
in drying the precipitate, wiped, and weighed against a counterpoise
of similar shape.
The substance to be analysed is weighed directly into the beaker
(or crucible) and dissolved in a suitable solvent. [The filter-stick is
kept outside the beaker until precipitation is complete.] The precipita-
tion reaction is then carried out in the normal way. When precipita-
tion is complete, the filter-stick may be inserted into the beaker (or
crucible) and used as a stirring-rod. The precipitate is allowed to
settle, all the supernatant liquid is sucked off through the filter-stick
by attaching the latter with rubber tubing to either of the receivers
depicted in Fig. XI, 4, 1; these are held in a small clamp attached to
a stand (compare Fig. XI, 4, 2) to ensure stability. This operation
must be carried out carefully using as little suction as possible; the
rate of filtration can be easily controlled with the aid of the stopcock.
The residual precipitate must be washed several times by successive
portions of the wash liquid, which should be introduced from a wash
826 Quantitative Inorganic Analysis
bottle or pipette down the sides of the micro-beaker or micro-crucible
and filter-stick. Finally, after sucking the residue as dryas possible,
the precipitation vessel, with the filter-stick inside it, is wiped externally,
placed in an appropriate dryingapparatus
(Benedetti -Pi()hler drier or thermostatically
controlled electric drying oven) and heated
for the requisite time. [Pyrex filter-sticks
should not be heated above 180 0 C.] The
apparatus is finally removed, allowed to
cool for 10 minutes in a metal block de-
siccator, wiped carefully with moist and
then dry chamois leather (Section XI, 2),
transferred to a micro- or semimicro-
balance, and weighed after 5-10 minutes.
The Miller micro-immersion filter or filter-
stick (1939), Fig. XI, 4,4, c, employs a filter-
paper disc of about 15 mm. thickness, and
is of particular value for the filtration of
gelatinous precipitates such as hydrated
silica, ferric and aluminium hydroxides.
The filter-disc is conveniently cut from a
Whatman "accelerator" by means of a
sharp cork borer.
It is constructed in the following manner.
Two pieces of Pyrex tubing are required,
namely, a 12-mm. length of capillary tubing of
35 mm. external diameter and 1 mm. bore, cut
(e)
off square, and a 150-mm. length of tubing of
1 mm. wall into which the capillary fits closely.
The longer tube is drawn out at one end to
form a capillary of 25 mm. external diameter
and 70 mm. length, and the thick capillary
IOmm. tube is pushed in at the other end as far as it
will go (Fig. XI, 4, 4, a). The pair of tubes
is then steadily rotated and heated at Z in a
small and not too hot blowpipe flame so as to
(0) (b)
fuse together the two pieces of glass with the
minimum of deformation. The heating is
FIG. XI, 4, 4.
gradually extended towards Y until the whole
of the capillary tube is sealed in without deforming the flat end at Y:
thereafter the size of the flame is increased a little, the capillary heated
more strongly towards X, and the tube, after slight blowing, is drawn out
to give the appearance shown in (b). The whole is then annealed. Finally,
. the tube is cut sharply at Z, and the piece of wider tubing removed, leaving
not more than 2 mm. projecting from the capillary. If the break is irregular
the tube is carefully ground flat and fire-polished without causing the glass
to collapse. The final form is shown in (c).
B. Filter beakers. This device (Fig. XI, 4, 5), due to E. Schwarz-
Bergkampf (1926), incorporates the filter-stick and beaker in one
vessel. The commercial apparatus is of Pyrex glass, about 27 mm.
in diameter and with a sintered-glass filter-disc (10 mm. diameter)
sealed into the outlet neck. It is first used as a beaker in which the
precipitation is carried out and then as a filter by which the precipitate
is retained. If desired, the filtrate may pass into a similar beaker
Micro-gravimetric and Micro-volumetric Analysis 827
(Fig. XI, 4, 6), possibly for a further step in a separation. The filter
beakers are, of course, weighed accurately with the usual precautions
before and after use. An interesting application of the filter-stick
and the filter-beaker will be evident from Fig. XI, 4, 7.
( b) (r)
FIG. XI, 4, 8.
FIG. XI, 4, 9.
ium or copper block about 8 cm. long with two holes, one 13 mm. and
the other 8 mm. in diameter; the lower block is drilled to accommodate
a thermometer. The whole is mounted on a rigid base and is heated
by a micro-burner. The filter-tube is dried directly in one of the
channels, usually that of 13 mm. diameter. A glass tube containing a
plug of pure cotton wool to act as an air-filter is placed in the wide end
of the filter-tube, and the stem is inserted into a short length of rubber
tubing which is connected by a glass tube and rubber tubing to a water-
pump. A slow stream of air is aspirated through the apparatus as
drying proceeds; the main body oHhe tube should be heated to llO C.
for not less than 15 minutes. [Alternatively, the Benedetti-Pichler
drier, Fig. XI, 3, 5, may be used.] When dry, the filter-tube is dis-
connected, wiped, and weighed after 15 minutes. In use, the filter-
tube is fitted to the siphoning system (Fig. XI, 4, 8, b or c) and gentle
suction applied: a test-tube or centrifuge tube is best employed as
the reaction vessel. The whole apparatus must be supported firmly.
When filtration is complete, the filter-tube is detached, dried, wiped,
and weighed.
D. Micro-crucibles. A small porous-porcelain filter-crucible (Ne-
bauer crucible, Section XI, 3F) is attached to a glass tube of the same
outside diameter as the bottom of the crucible by means of a short
rubber sleeve (Fig. XI, 4, 10). The glass tube is fitted by means of a
Micro-gravimetric and Micro-volumetric Analysis 829
rubber stopper into a 250-ml. filter-flask as in Fig. XI, 4, 8, b. Filtra-
tion may be carried out with the aid of gentle suction from a water-
pump or by suction with the mouth through a 50-cm. length of rubber
tubing attached to the side arm of the filter-flask. The
siphon technique, described under Filter-tubes, is not
always successful, especially when dealing with fine pre-
cipitates. The precipitate may be transferred from the
precipitation vessel to the micro-crucible by means of
a rubber-capped dropping pipette; the latter may be 8 cm.
long, 5 mm. in diameter, and narrows sharply to a capill-
ary of I mm. bore and 3 cm. in length. After the trans-
fer of the precipitate and of the wash liquid, the rubber
cap is removed and the pipette is rinsed with distilled water
and alcohol.
In practice, it is found that most of the operations re-
quiring the use of micro-crucibles can be carried out with
a filter-stick constructed of appropriate material to with- F x
stand the necessary temperature. Thus barium sulphate IG. J, 4, 10.
may be precipitated in the presence of agar (Section IV, 6); the re-
sulting crystalline precipitate is readily handled by the filter-stick
technique.
XI, 5. Apparatus for micro-volumetric analysis.-Small quantities of
liquids or substances may be titrated either with very dilute standard
solutions or with small volumes of standard solutions of concentrations
such as are employed in macro-analysis. The use of very dilute
standard solutions is usually limited by the indefinite end points
and by the solubility effects obtained under such conditions. Micro-
titrations are therefore generally carried out with small volumes (e.g.,
1-10 ml.) of solutions of the usual strengths (e.g., 001-0IN). Thus it is
more accurate to titrate with O'OIN solutions from a 2-ml. micro-
burette than to use O'OOIN solutions from a 25-ml. burette. If the
stability of the indicator permits, it is often convenient to incorporate
it in the standard solution. The various apparatus employed for
semi-micro (centigram, i.e., 1-10 cg. of sample) procedures will now be
described together with selected apparatus for micro (milligram, i.e.,
1-10 mg. of sample) procedures: emphasis will, however, be laid on
semi-micro-apparatus. From the viewpoint of the student's initial
training in micro-titrimetry, centigram procedures are to be preferred,
particularly as a good semimicro-balance suffices, and comparatively
inexpensive, commercially available apparatus may be used.
A. Volumetric flasks. Volumetric flasks are employed to prepare a
definite volume of solution from a given weight of material. If sufficient
of the material is available, especially if it is likely to be very hetero-
geneous, it is preferable to dissolve a relatively large sample in a large
volumetric flask, and to employ a small aliquot portion for the analysis.
If, however, only a small weight of the substance is given for the analysis,
volumetric flasks of capacities of 1-25 ml. must be used. Ground-
stoppered Pyrex volumetric flasks of 1 and 2 ml. capacity (test-tube
shape) -and 5, 10, and 25 ml. capacity (standard form) may be purchased.
It is important that the graduation mark be so placed that adequate
mixing is possible; care must also be taken that liquid is not trapped
by, or leaks past, the stopper. The micro-volumetric flasks shown in
Fig. XI, 5, 1 have been designed to reduce these possible errors to a
830 Quantitative Inorganic Analysis
mmlmum. In type (a) the upper part has three to five times the
capacity of that of the calibrated part; mixing is facile, but there is a
tendency for the flask to tip over easily and, in consequence, it must
(a) (6)
FIG. XI, 5, 7. FIG. XI, 5, 8.
Ac Neptunium [237] i
Actinium 89 227 Np 93
Aluminium . Al 13 2697 Neon Ne 10 20183
Americium Am 95 [241] Nickel Ni 28 5869
Antimony Sb 51 12176 Niobium
Argon A 18 39944 (Columbium) Nb 41 9291
Arsenic As 33 7491 Nitrogen N 7 14008
Astatine At 85 [210] Osmium Os 76 1902
Barium Ba 56 13736 Oxygen. 0 8 160000
Beryllium Be 4 9013 Palladium Pd 46 1067
Bismuth Bi 83 20900 Phosphorus P 15 3098
Boron B 5 1082 Platinum Pt 78 19523
Bromine Br 35 79916 Plutonium Pu 94 [239]
Cadmium Cd 48 11241 Polonium Po 84 210
Caesium Cs 55 13291 Potassium K 19 39096
Calciu..'U Ca 20 4008 Praseodymium Pr 59 14092
Carbon C 6 12010 Promethium Pm 61 [147]
Cerium Ce 58 14013 Protoactinium Pa 91 231
Chlorine CI 17 35457 Radium Ra 88 226'05
Chromium Cr 24 5201 Radon Rn 86 222
Cobalt Co 27 5894 Rhenium Re 75 18631 I!
Copper Cu 29 6354 Rhodium Rh 45 10291
Curium Cm 96 [242] Rubidium Rb 37 8548
Dysprosium. Dy 66 16246 Ruthenium Ru 44 1017
Erbium Er 68 1672 Samarium Sm 62 15043
Europium Eu 63 1520 Scandium Sc 21 4510
Fluorine F 9 1900 Selenium Se 34 7896
Francium . Fr 87 [223] Silicon Si 14 2806
Gadolinium. Gd 64 1569 Silver Ag 47 107880
Gallium Ga 31 6972 Sodium . Na 11 22997
Germanium. Ge 32 7260 Strontium Sr 38 8763
Gold Au 79 1972 Sulphur . S 16 32066
Hafnium Hf 72 1786 Tantalum Ta 73 18088
Helium He 2 4003 Technetium '}'c 43 (99)
Holmium Ho 67 16494 Tellurium Te 52 12761
Hydrogen H 1 10080 Terbium Tb 65 1592
Indium In 49 11476 Thallium TI 81 20439
Iodine I 53 12692 Thorium Th 90 23212
Iridium Ir 77 1931 Thulium Tm 69 1694
Iron Fe 26 5585 Tin Sn 50 11870
Krypton Kr 36 837 Titanium Ti 22 4790
Lanthanum. La 57 13892 Tungsten
Lead Pb 82 20721 (Wolfram) W 74 18392
Lithium Li 3 6940 Uranium U 92 23807
Lutetium . Lu 71 17499 Vanadium V 23 5095
Magnesium. Mg 12 2432 Xenon Xe 54 1313
Manganese Mn 25 5493 Ytterbium Yb 70 17304
Mercury Hg 80 20061 Yttrium Y 39 8892
Molybdenum Mo 42 9595 Zinc Zn 30 6538
Neodymium Nd 60 14427 Zirconium Zr 40 9122
* A value given in brackets denotes the mass number of the most stable known
isotope.
841
842 Quantitative Inorganic Analysis
A,2. CHEMICAL FACTORS *
Sought. Found. Factor. Log Factor.
\ \ I I
Pb PbSO. 068325 1,83458
PbCrO. 064108 180691
PbMo0 4 056436 1,75156
Pb(C 7 H s02N) 060529 178197
Pb(IO a)2 - 037198 1,57052
Pb0 2 086623 }93763
I
Ag I AgCl 075263 }87658
As As 2 S S 060903 1,78463
Mg(NH.)AsO.,6H2O 025887 1,41309
Mg 2As 20 7 048258 1,68356
UaOs 026683 1,42624
Sb Sb 2S S 071687 .185544
Sb 2O. 079189 1,89866
049739 169669
Sn
SbCsHaOa
Sn0 2
-
078766 }89634
Al A1 20 s 0-52913 1-72357
Al(CgHSON)s 0-05871 276868
I
Be I BeO 0-36051
I
1,55692
Zn
[Co(CsHsN).J(CNSh
Zn(NH.)PO.
I 0-11992
036648
1-07890
1,56405
Zn 2P 20 7 042912 1-63257
ZnS 0-67098 1 -82671
Zn(CloHs02N)2,HzO 015286 1-28699
[Zn(C 5H sN)2J(CNS)2 019245 Y28431
Zn(C 7H s0 2N)2 019364 Y'28699
Zn(C 1oH g ON)2 017132 1-23380
\
Mn Mn2 PkO,
I 038708
I 1'58780
Th Th0 2
I 087884 1-94391
Ca CaC 20 4 ,H zO
I 027430 1,43822
CaCOs I 040044 160254
CaO 0-71469 1'85412
CaMoO. 020037 130183
CaW0 4 013917 1'14354
W WO s 0-79303 1-89929
W0 2 (C g H 6ON)2 0-36477 1-56202
BaW0 4 0-47737 1-67885
Anions
CI AgCI 0-24737 1-39334
_'
Appendix 849
14. Water Analysis
Therou, Eldridge, and MaIlman. Laboratory Manual for Ohemical and
Bacteriological Analysis of Water and Sewage. Third Edition. McGraw-
Hill, 1943.
Standard Methods for the Examination of Water and Sewage. American
Public Health Association, New York, 1946.
E. W. Taylor. The Examination of Water and Water Supplies (Thresh, Beale,
and Suckling). Sixth Edition. Churchill: Blakiston, 1949.
Approved Methods for the Physical and Ohemical Examination of Water.
Institution of Water Engineers, London, 1949.
15. Reagents
" AnalaR " Standards for Laboratory Ohemicals. Fourth Edition. British
Drug Houses, Poole, and Hopkin and Williams, London, 1949.
Specifications for Analytical Reagents. Recommended by the Committee on
Analytical Reagents of the American Chemical Society. American
Chemical Society, Washington, D.C., 1951.
J. Rosin. Reagent Ohemicals and Standards. Second Edition. Van
Nostrand, 1946.
16. General Industrial Analysis
A. H. Allen. Oommercial Organic Analysis. Fifth Edition. Volumes 1-10.
Churchill, 1924-33.
C. A. Keane and P. C. L. Thorne. Lunge and Keane's Technical Methods of
Ohemical Analysis. Volumes I-IV. Gurney and Jackson, 1924-40.
W. W. Scott and N. H. Furman. Standard Methods of Ohemical Analysis.
Volume II. Special Subjects. Fifth Edition. Van Nostrand.
F. D. Snell and F. M. Biffen. Oommercial Methods of Analysis. McGraw-
Hill, ] 944.
Bibliography of Standard Tentative and Recommended or Recognised Methods
of Analysis. Society of Public Analysts, London, 1951.
17. Agricultural Analysis, Food Analysis, etc.
E. G. Mahin and R. H. Carr. Quantitative Agricultural Analysis. McGraw-
Hill, 1923.
C. W. Wright. Agricultural Analysis. T. Murby, 1938.
Official and Tentative Methods of Analysis. Sixth Edition. Association of
Official Agricultural Cht;mists, Washington, D.C., 1945.
A. G. Woodman. Analysis of Foods. Fourth Edition. McGraw-Hill,1941.
J. R. Nicholls. Aids to Analysis of Foods and Drugs. Sixth Edition.
Bailliere, Tindall and Cox, 1942.
A. L. Winton and K. B. Winton. Analysis of Foods. J. Wiley: Chapman
and Hall, 1945.
H. E. Cox. The Ohemical Analysis of Foods. Fourth Edition. Churchill,
1950.
M. A. Joslyn. Methods in Food Analysis Applied to Plant Products.
Academic Press, 1950.
J. Grant. A Laboratory Handbook of Pulp and Paper Manufacture. Arnold,
1942.
Improved Methods for the Quantitative Analysis of Coal Ash and Coke Ash.
Department of Scientific and Industrial Research. Fuel Research.
Survey Paper, No. 50. His Majesty's Stationery Office, London, 1949.
18. Apparatus, etc.
Much valuable information concerning apparatus is to be found in the
catalogues of various manufacturers. A selected list is given below.
Baird and Tatlock (London), Ltd., Freshwater Road, Chadwell Heath, Essex.
A. Gallenkamp and Co., Ltd., 17-29, Sun Street, London, E.C.2.
850 Quantitative Inorganic Analysis
Griffin and Tatlock, Ltd., Kemble Street, Kingsway, London, E.C.2.
George and Becker Ltd., Hatton Wall, London, E.C.2.
Townson and Mercer, Ltd., Croydon, Surrey.
J. W. Towers and Co., Ltd., Victoria Works, Widnes, Lanes.
Jencons (Scientific), Ltd., Rosebank Works, Rosebank Way, Acton, London,
W.3.
Fisher Scientific Co., 717 Forbes Street, Pittsburgh 19, Pa.
Eimer and Amend, Greenwich and Morton Streets, New York 14, New York.
E. H. Sargent and Company, 4647 W. Foster Avenue, Chicago 30, Illinois.
Central Scientific Company, 1700 Irving Park Road, Chicago 13, Illinois.
Arthur H. Thomas Company, West Washington Square, Philadelphia 5, Pa.
Will Corporation, Rochester 3, N.Y.
Wilkens-Anderson Co., 4525 W. Division Street, Chicago 51, Illinois.
Some firms publish booklets from time to time in which recent improve-
ments in laboratory apparatus and technique are described, for example:
Bulletin and Laboratory Notes (Baird and Tatlock (London), Ltd.).
The Laboratory (Fisher Scientific Co.).
19. Chemical and Physical Constants
E. W. Washburn, et al. International Critical Tables. 7 Volumes.
McGraw-Hill, 1926-30.
H. Landolt and R. Bornstein. Physikalisch-Ohemische Tabellen. Fifth
Edition. 9 Volumes. J. Springer, Berlin, 1923-50: Edwards Brothers,
Ann Arbor.
J. D'Ans and E. Lax. Taschenbuch fur Ohemiker und Physiker. Springer-
Verlag, Berlin, 1943.
N. A. Lange. Handbook of Chemistry. Seventh Edition. Handbook
Publishers, 1949.
C. D. Hodgman. Handbook of Ohemistry a1W, Physics. Thirty-first Edition.
Chemical Rubber Co., 1949.
G. W. C. Kaye and T. H. Laby. Tables of Physical and Ohemical Constants.
Tenth Edition. Longmans, Green, 1948.
E. Hope. The Chemists' Year Book. John Sherratt, Son and Co., Timperley,
1949.
A. Seidell. Solubilities: A Oompilation of Quantitative Solubility Data from
the Periodical Literature! Third Edition. Volume 1. Solubilities of
Inorganic and Metal Organic Compounds, 1940. Volum(;II. Solubilities
of Organic Compounds, 1941. Van Nostrand.
S. Miall and L. M. Miall. New Dictionary of Chemistry. Second Edition.
Longmans, Green, 1949.
F. M. Turner. The Condensed Chemical Dictionary. Fourth Edition.
Reinhold, 1950.
20. Journals r
A list of the most important Journals in which the results of original
research in analytical chemistry are published is given below. .Many
memoirs on chemical analysis appear in numerous other scientific journals;
abstracts of these may be found in the British Chemical Abstracts published
by the Bureau of Chemical Abstracts, London, or in Chemical Abstracts
published by the American Chemical Society. Valuable summaries appear
in the Annual Reports on the Progress of Chemistry published by the Chemical
Society, London. An Annual Review of Analytical Chemistry (commenced
1949), covering the various branches of Fundamental Analysis and aIm
Applications of Analytical Developments, appears in the January and
February issues of Analytical Chemistry, published by the American Chemical
Society. This provides an excellent means of keeping in touch with recent
developments.
Appendix 851
The Analyst.
Industrial and Engineering Chemistry, Analytical Edition. (The name was
changed on January 1st, 1947, to Analytical Chemistry.)
A nnales de Chimie analytique et de Chimie appliquee et Revue de Chimie
analytiqtte reunies.
Zeitschrift fur analytischen Chemie.
Journal of the Chemical Society.
Journal of the Society of Chemical Industry. (The name was changed on
January 1st, 1951, to Journal of Applied Chemistry.)
J Gurnal of the American Chemical Society.
Bulletin de la Societe chimique de France.
Berichte der deutschen chemischen Gesellschaft.
Recueil des Travaux chimiques des Pays-Bas et de la Belgique.
Journal of Research of the National Bureau of Standards.
A,4. DENSITIES OF ACIDS AT 20 C.
(DENSITIES AND PERCENTAGES BY WEIGHT ARE BASED ON WEIGHTS IN V AC[;O.
AND THE PERCENTAGE BY WEIGHT REFERS TO THE FORMULA GIVEN.)
Per Cent
by If' eight.
I~- Density.
I
H 2 SO 4 ,
i HNO a I HC H a0
2 2 H aP0 4
I HCI.
i
1 10051 10036 09996 10038 10032
2 10ll8 10091 10012 10092 10082
3 10184 10146 10025 - -
4 10250 1.0201 10040 10200 10181
5 10317 10256 10055 - -
6 10385 10312 10069 10309 10279
7 10453 10369 10083 - -
8 10522 10427 10097 10420 10376
9 10591 10485 l'Olll - -
10 10661 10543 10125 10532 10474
11 10731 10602 10139 - -
12 10802 10661 10154 10647 10574
13 10874 10721 10168 - -
14 10947 10781 10182 10764 10675
15 11020 10842 10195 - -
16 11094 10903 10209 10884 10776
17 1-1168 10964 10223 - -
18 11243 1-1026 10236 11008 10878
19 1-1318 H088 10250 - -
20 11394 1-1150 10263 11134 10980
21 1-1471 11213 10276 I - -
22 1-1548 11276 10288 11263 11083
23 11626 1-1340 10301 - -
24 11704 11404 10313 11395 1-1187
25 11783 1-1469 I 10326 - -
26 11862 11534 10338 l-l529 11290
27 11942 11600 10349 - -
28 12023 11666 10361 1-1665 11392
29 12104 1-1733 10372 - -
30 12185 11800 10384 1-1805 l-l493
31 12267 1-1867 10395 - -
32 12349 11934 10406 - 1-1593
33 12432 12002 10417 - -
34 12515 12071 10428 - 1-1691
35 12599 12140 10438 1216 -
36 12684 12205 10449 - 1-1789
37 12769 12270 10459 - -
38 12855 12335 10469 - 11885
39 12941 12399 10479 - -
40 13028 12463 10488 1254 11980
852 Quantitative Inorganic Analysis
DENSITIES OF ACIDS AT 20 C.-Continued
Den8ity_ J
Per Cent
~
by Weight. H 2 SO 4_ HNO a _ H'C 2H a0 I H SP 04-
I 2-
,
A.6. DATA ON THE STRENGTH OF AQUEOUS SOLUTIONS OF
THE COMMON ACIDS AND OF AMMONIUM HYDROXIDE
Ferro Alloys
No. 202, Ferro Tungsten, low C Vv
tungsten
No. 231, Ferro- Molybdenum, low C 1\10
molybdenum
No. 203, Ferro- Chromium, low C and Cr, S, Cd. C"
chromium S
No. 204, Ferro- Chromium, high C and Cr, S, Cd. C
chromium S
No. 205, Ferro- Vanadium standard V
vanadium only
No. 208, Ferro- Complete analysis Si, S, P, Mn, AIJ,.Ni,-Fe, Ti,
manganese Cr, Cd. C, Total C
No. 201, Ferro- Titanium, low C Ti
titanium
Slag
No. 174, Basic slag P 20 S and part P 2 0 S , Si0 2 , CaO, MgO, Fe,
analysis
Ores
, Mn
No. 175, Iron ore Complete analysis Fe, P, CaO, MgO, Alkalis,
and volumetric Si0 2 , A1 2 0 3 , Ti0 2 , S, Cd.
standard H 20, CO 2
No. 176, Manganese Mn, 0, Si0 2 , P, Fe Fe, P, Mn, 0, Si0 2
ore
Non-Ferrous Alloys
No. 177, White metal Complete analysis Pb, Sb, Sn, Cu, Bi, As, Zn, Fe
No. 178, White metal Complete analysis Pb, Sb, Sn, Cu, Fe, As, Zn
No. 179, Manganese Complete analysis Pb, Sn, Cu, Fe, Mn, Zn, lfi,
brass Al
No. 180, Cupro-nickel Complete analysis Cu, Fe, Mn, Ni, Mg, Si
No. 181, Aluminium Complete analysis Pb, Cu, Fe, Zn, Ni, Mg, Sn,
alloy AI, Si
No. 182, Aluminium Complete analysis, Si, Fe, Al
alloy high Si
No. 216, Aluminium General purpose Si, Sn, Cu, Fe, Bi, Ti, Zn, Ni,
alloy Mg
No. 183, Bronze con- Complete analysis Pb, Sb, Sn, Cu, Fe, As, Zn,
taining P Ni, P
No. 207, Bronze Complete analysis Pb, Sb, Sn, Cu, Fe, As, Zn,
Ni,P, S
Pure Standardised Reagents and Metals
Benzoic acid, Ko. 190e Purity 9993 %
Tin, No. 192b Purity 99'96%. M.p. 2319 C.
Lead, No. 210 Purity 9999%. lVI.p. 3273 C.
Zinc, No. 194a Purity 9999%. M.p. 4194 C.
Aluminium, No. 195a Purity 99'84%. M.p. 6592 C.
Aluminium, No. 198 Purity 9999%.
Copper, No. 197b Purity 9990%. M.p. 1083 C.
Molybdenum, No. 227 Purity 99'9%.
r------,------------------------,\--------------------------~~
Steels
8g Bessemer, 01 C C, Mn, P, S, Si, Cu, Ni
10e Bessemer, 04 C C, Mn, P, S, Si, Cu, Ni, Cr, Mo
220 Bessemer, 06 C, aluminium C, Mn, P, S, 8i, Cu, Al
bearing
15d B.O.H., 01 C C, Mn, P, S, Si, Cu, Ni, Cr
Ilf B.O.H., 02 C C, Mn, P, S, Si, Cu, Ni, Cr, Mo
12e B.O.H., 04 C C, Mn, P, S, Si, Cu, Ni, Cr, Mo
152 B.O.H., 05 C, 004 Sn C, Mn, P, S, Si, Cu, Ni, Cr, Mo, Sn
13e B.O.H., 06 C C, Mn, P, S, Si, Cu, Ni, Cr, Mo
14c B.O.H., 08 C C, Mn, P, S, Si, Cu, Ni, Cr, Al
16c B.O.H., 10 C C, Mn, P, S, Si, Cu, Ni, Cr
1ge A.O.H., 02 C C, Mn, P, S, Si, Cu, Ni, Cr, Mo, Sn
20e A.O.H., 04 C C, Mn, P, S, Si, Cu, Ni, Cr, Mo, Sn
21d A.O.H., 06 C, 008 Sn C, Mn, P, S, Si, Cu, Ni, Cr, Mo, As, Sn
34a A.O.H., 08 C C, Mn, P, S, Si, Cu, Ni, Cr, Mo
35a A.O.H., 10 C C, Mn, P, S, Si, Cu, Ni, Cr, Mo, V
51a Electric furnace, I 2 C C, Mn, P, S, Si, Cu, Ni, Cr, Sn
65c Basic electric, 03 C C, Mn, P, S, Si, Cu, Ni, Cr
100a Manganese C, Mn, P, S, Si, Cu, Ni, Cr, Al
* These are issued jointly by the Iron and Steel Institute and the National Physical
Laboratory, and are obtainable from the National Physical Laboratory, }\.fetallurgy
Department, Teddington, Middlesex, England.
t Obtainable from the U.S. Department of Commerce, Bureau of Standards,
\Vashingtoll, D.C., U.S.A.
t Metals present in quantities less than 001 per cent are not indicated. The data
have been extracted from Supplement to National Bureau of Standards Circular 398,
issu(ld January 1, 1949.
862 Quantitative Inorganic Analysis
Standard Samples Issued by the U.S. National Bureau of Standards-
Continued
'------~--------------------.-----~~---------------.I
Steels-Continued
105 High-sulphur, 02 C (carbon C
only)
125 High-silicon, 50 Si C, Mn, Cu, Ni, Si, Cr, Al
129a High-sulphur C, Mn, S, P, Si, Cu, Ni, Cr
130 I Lead-bearing, 02 Pb C, Mn, S, P, Si, Cu, Cr, Pb
151 I
Boron-bearing, 0003 B B
33c Nickel C, Mn, P, S, Si, Cu, Ni, Cr, Mo, Al
32d Cr-Ni C, Mn, P, S, Si, Cu, Ni, Cr, Mo
72d Cr-Mo C, Mn, P, S, Si, Cu, Ni, Cr, Mo
lIla Ni-Mo C, Mn, P, S, Si, Cu, Ni, Cr, Mo
30d Cr-v C, Mn, P, S, Si, Cu, Ni, Cr, V, Mo
139, 156 Cr-Ni-Mo C, Mn, P, S, Si, Cu, Ni, Cr, Mo
106a Cr-Mo-Al (Nitralloy G) C, Mn, P, S, Si, Cu, Ni, Cr, Mo, Al
36 Cr 2-Mo 1 C, Mn, P, S, Si, Cu, Ni, Cr, Mo
135 Cr 5-Mo 05 C, Mn, P, S, Si, Cu, Ni, Cr, V, Mo
159 Cr I-Mo O4---Ag 01 C, Mn, P, S, Si, Cu, Ni, Cr, V, Mo,
Ag
SOb W lS-Cr 4---V 1 C, Mn, P, Si, Cu, Ni, Cr, V, Mo, W,
As, Sn
132 Mo 7-W 6---Cr 4---V 15 C, Mn, P, Si, Cu, Ni, Cr, V, Mo, W
134 Mo 9-W 2-Cr 4-V 1 C, Mn, P, Si, Cu, Ni, Cr, V, Mo, W
153 Mo S-W 15-Cr 4-V 2-Co S C, Mn, P, Si, Cu, Ni, Cr, V, Mo, W,
Co
155 Cr O5-WO5 C, Mn, P, S, Si, Cu, Ni, Cr, V, Mo, W
73a Stainless (Or 14) C, Mn, P, S, Si, Cu, Ni, Cr, Y, Mo, W
133 Stainless (Cr 14-Mo O'6---S 0'4) C, Mn, P, S, Si, Cu, Ni, Cr, V, Mo
101c Cr lS-Ni 9 C, Mn, P, S, Si, Cu, Ni, Cr, V, Mo,
Co, Cb
121a Cr lS-Ni 10 (Ti-bearing) C, Mn, P, S, Si, Ou, Ni, Cr, V, Mo,
Co, Ti
123a Cr lS-Ni 11 (Cb bearing) P, Si, V, Mo, W, Cb
160 Cr 19-Ni'~-=Mo 3 C, Mn, P, S, Si, Cu, Ni, Cr, V, Mo
166 (Cr 19-Ni 9 (carbon only) C
126a High nickel (Ni 36) C, Mn, Si, Cu, Ni, Cr, Co
161 Casting alloy (Ni 64---Cr 17-Fe
15)
Irons
4g,5i Cast iron Total C, Gr. C, * Mn, P, S, Si, Cu, Ni,
Cr, V, Mo, Ti, As
6e Cast iron Total C, Gr. C, Mn, P, S, Si, Cu, Ni,
I
Cr, Y, Mo, Ti
82a
115
Nickel-chromium cast iron I
C, Gr. C, Mn, P, S, Si, Cu, Ni, Cr,Y, Ti
Nickel-chromium-copper cast C, Mn, P, S, Si, Cu, Ni, Cr, Co, Ti
122b
iron
Cast iron (car wheel)
I
C, Mn, P, S, Si, Cu, Ni, Cr, V I
55b Ingot iron C, Mn, S, Cu, Ni
107a I
Chromium-nickel-molybdenum C, Gr. C, Mn, P, S, Si, Cu, Ni, Cr, \
cast iron Y, Mo, Ti
Steel-making Alloys
57 Refined silicon C, Mn, Si, Ti, AI, Ca, Fe, Cr
58 Ferrosilicon (75 % Si) C, Mn, P, S, Si, Ti, AI, Ca, Fe, Cr
59 Ferrosilicon (50 % Si) C, Mn, P, Si, V, Ti, AI, Ca, Fe, Cr
61a Ferrovanadium (high carbon) C, Mn, P, Si, Cr, V, Al
64a Ferrochromium (high carbon) C, Mn, P, S, Si, Cr, V
66a Spiegeleisen C, Mn, P, S, Si
67 Manganese metal C, Mn, P, Si, Ni, Cr, V, Fe
68a Ferromanganese C, Mn, P, S, Si, Cr, V
71 Calcium molybdate Mo = 3530; Fe = 1'92; Ti = 006
75a Ferrotungsten W
90 Ferrophosphorus P
116a Ferrotitanium (low carbon) C, Si, V, Ti, AI, C
Non-ferrous Alloys
8.'5a Aluminium alloy, wrought Cu, Mn, Si, Mg, Fe, Ti, Zn, Ga, Ni,
I
Cr
86c Aluminiumbase casting alloy Cu, Mn, Si, Fe, Ti, Zn, Pb, Ni, Cr
87 Aluminium-silicon alloy Cu, Mn, Si, Mg, Fe, Ti, Zn, Pb, Sn,
Ni, Cr
37d Brass, sheet Cu, Zn, Sn, Pb, Ni, Fe
164 Brass, aluminium Cu, Zn, AI, Mn, Fe, Sn, Pb, Ni, Si
52b ' Bronze, cast Cu,Zn,Sn,Pb,Ni,Fe
62b Bronze, manganese Cu, Zn, Sn, Pb, Ni, Fe, AI, Mn
63b Bronze, phosphorus Cu, Zn, Sn, Pb, Ni, Fe, Al
158 Bronze, silicon Cu, Si, Zn, Fe, Mn, Sn, Al
157 Nickel silver (Cu 72-Ni 18-Zn Cu, Zn, Pb, Ni, Fe, Mn
10)
124b Ounce metal (Cu 85-Pb 5-Sn Cu, Zn, Sn, Pb, Ni, Fe
5--Zn 5)
53c Lead-base bearing metal Sb, Sn, Cu, Bi, As
127 Solder (Pb 65--Sn 35) Sn, Sb, Bi, Cu, As
54c Tin -base bearing metal Pb, Sn, Sb, Bi, Cu, Fe, As, Ag, Ni
162 Monel type (Ni 66-Cu 29) Ni, Cu, Mn, Si, Co, Fe, Cr, AI, Ti, C
161 Nickel-base casting alloy Ni, Cu, Mn, Si, Co, Fe, Cr, C, P
94a Zinc-base die-casting alloy AI, Cu, Mg, Fe, Mn
108 Zinc spelter Pb,Cd,Fe
109 Zinc spelter Impurities <01 % -
llO Zinc spelter Pb,Cd,Fe ~
Ceramic Materials
104 Burned magnesite Si0 2 , Fe 20 a, AI 2 0 s, Ti0 2 , MnO, CaO,
MgO, Nap
76 Burned refractory (40% AlzOa) AI 2 0 a, Fe 20 a, Si0 2 , Ti0 2 , Zr0 2
77 Burned refractory (60% AlzOs) AlzO a, FezO a, Si0 2 , Ti0 2 , Zr0 2
78 Burned refractory (70 % AI 2i)a) A1 2 0 3 , Fe Z0 3 , Si0 2 , Ti0 2 , Zr0 2
103 Chrome refractory CraGs, Si0 2 , FeO, AI 2 0 s , CaO, MgO,
Ti0 2
97 Clay, flint Si0 2 , A~03' Ti0 2 , Zr0 2 , Fe2 0 S '
P 20 S' Vr.q s' Cr 2 0 S ' K 2 0
98 Clay, plastic SiO a, A'~s' Ti0 2 , Zr0 2 , FeaOs,
PzOs, VzOs, CrzOg, KzO
70 Feldspar, potash R 20, Na 2 0, Si0 2 , AI 2 0 a, Fe 2 0 a, CaO,
MgO
99 Feldspar, soda R 20, Na 20, Si0 2 , AI 20 a, FeaO a, CaO,
MgO, Ti0 2
79 Fluorspar CaF 2 , CO 2 , Si0 2 , Zn, Pb, S, Fc2 0 a ,
AI 2 0 a, K 20, Na 2 0, MgO, BaO
92 Glass, low boron B 20 3
93 Glass, high boron Si0 2 , AI 2 0 a, Fe 2 0 a, Ti0 2 , Zr0 2 ,
MgO, K 2 0, N a 2 0, B 2 0 a, As 2 0 a, CI
139 Glass, lead-barium Si0 2 PbO, AI 2 0 a Fe 2 0 a, MnO,
Ti0 2 , CaO, BaO, MgO, K 2 0,
NazO, P 2 0 S ' As 2 0 a, As 2 0 S ' SOa, CI
III Glass, opal SiO z, PbO, AlzOa, Fe Z0 3 , ZnO, Ti0 2 ,
ZrO z, CaO, K 2 0, Na 2 0, PaOs,
As 2 0 a, As 2 0" Cl, F
130 Glass, soda-lime SiO a, AlzO a, Fe 20 a, Ti0 2 , CaO, MgO,
KzO, Na 20, As 2 0 a, As 2 0 S ' SOa, CI
128 Glass, soda-lime (B 2 0 3 , BaO) SiO z, AlzOs' FezDa' TiO z, CaO, BaO,
l\IgO, KaO, Na 2 0, B 2 0 a, PaOs,
TiO z, ZrO z, BaO
131 Glass sand FeaO a, AlaO s , Ti0 2 , ZrO z, CaO. MgO
165 Glass sand (low iron) Fe 2 0 S
la Limestone, argillaceous Si0 2 , Fe 20 a, A1 20 a, Ti0 2 , MnO, CaO,
SrO, MgO, Na 2 0, K~O, S03' S,
P 2 0 S' CO 2 , C
138 Limestone, dolomitic Si0 2 , Fe 2 0 a, AI 2 0 a, CaO, MgO,
Na 20, K 20, S03' S, CO 2 , C
1()2 Silica brick Si0 2 , Fe 2 0 3 , AI 20 s , Ti0 2 , CaO, MgO,
Na2 0, K 2 0, PzOs
112 Silicon carbide Total Si, Total C, Free C, SiC, Fe,
AI, Ti, Zr, Ca, Mg
154 Titanium dioxide TiO z
Spectrographic Standards
401-430 Steels; 4-in. rods The twenty steel samples cover
801-830 Steels; 8-in. rods varying proportions of Mn, Si,
Cu, Ni, Cr, V, Mo, AI, Sn, and
B; also 0007 % Co and 052 %
W
601-604 Aluminium alloys; discs two- The four alloys cover varying pro-
and-a-half in. in diameter portions of Cu, Mg, Si, Mn, Fe,
Cr, and Ti; also 200 % Ni and
0029% Zn
Appendix 865
Standard Samples Issued by the U.S. National Bureau 0/ Standards-
Continued
Sample
No. Name. Intended Use.
I
1 - -I - - -
Chemicals
84d Acid :Jotassium phthalate (purity Acidimetric value
by titration, 10005 %)
39f Benzoic acid (purity by titration, Acidimetric and calorimetric
10003%) valuei'!
40e Sodium oxalate (purity by titra- Oxidimetric value
tion, 9996 %)
83a Arsenic trioxide (purity by titra- Oxidimetric value
tion, 99'99%)
136 Potassium dichromate (purity by Oxidimetric value
titration, 10000 %)
17 Sucrose or cane sugar (purity, Calorimetric and saccharimetric
9999%) values
41 Dextrose or glucose (purity, Reducing value
9999%)
Microchemical Standards
140 Benzoic acid 1 For C and H determination
141 Acetanilide For N, C, and H determination
142 Anisic acid For methoxyl determination
143 Cystine For S, C, H, and N determination
144 2-Chlorobenzoic acid For Cl determination
145 2-Iodobenzoic acid For I determination
146 I Tri-a-naphthyl phosphate I For P determination
pH Standards
185 Acid potassium phthalate pH (approx.) 40
186Ia Potass~um dihydrogen phosphate } H (a ox ) 6.8 *
186IIa PotasslUm hydrogen phosphate p ppr.
187a Borax pH (approx.) 92
Melting-point Standards
44d Aluminium 659'7 C.
45b Copper 10832 C.
49c Lead 32731C.
428 Tin 23190 C.
43f Zinc 41950 C.
. Turbid.:luJ.e&ric ~ I'iIleness Standards
47i Cement
114 I Cement INo. 200 sieve residue, 94 %
No. 325 sieve residue, 96 %
Thermoelectric Standards
118 Alumel wire, No.8 gauge e.m.f. VS. NBS Pt No. 27, 0-
1300 C.
119 Chromel wire, No. 8 gauge e.m.f. VS. NBS Pt No. 27, 0-
1300 C.
0> r- -..1
II
< --:-"'"
-,j< l...,.,C-l
E-c Q.~ <:,
0> [~ [?<:'?~ [
~~o,.....,
[ [ [ [ [ [% [ [ [2 [ [ ??
00 [ 1 1 1 [ [ [ 1 1 [ [ 1 1 1
I
~ ~"
r;<:I ~ --
-,j< Ot-~Cl
...... r- "" M
. __ ~:
~ ;It; 1 ......
+',D
:sr;<:I ~~
0
0
Ir-""
~e:l
[?~?<:'
,.....,10000
0
[~ [ I~~!! [: [ [lC~ [6
M
[ [ [~ [% [ [ [~ [: [ I
I
0..00
E-c S
00 M-,j< t-~OOI""""'l lC MlCO""
...... ...... lC 0> r- lC lC -,j<
;l
--
lC
"" """
Ul +'il
'" 0
lC
P ",;>, -,j<
0t-I ..c:..c:
+'"
..,CIl
<:,
t- I 16:M
1?C:-9'7'~ [ [
OO~lO""'"
~<:o~,.....,1..O
0
[ood: [;...... [ [ [ [ [ [ [6 [ [ [6 -,j<
[ [ [~ [
lC
[ [ [~
<0
I
~
:::!-,j<
CIl ..c:
'" _-I """
< ....
:>- +'"'+'
...
; 0
E-c I ~'?~C?~
t-lQlOCCOO
< "Os
CIl
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......
~
b05'o
o~
r;<:I ~ ..... o
o
E-c ,,15 lC
< '0'"'" .~
~ '>0..
"~ OM
-I>< -,j< 0<0
Z
t-I ~ '" o
o [ ~~ ~~99
.~ 00 OOM~OOOI""""l
'0 t-~_.t- "o:t\
Ul
.~
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~ ].8 ""
zp CIl
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o
0 " '" M
~ ..c:-l
:s
0
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:.2~'
i: ..:
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0""
o
o
0
t;
t-I
"oj! 00
""
Z ,D
<
~
;l;>,
"',D o
o
~ ;lil ......
0 ~ i:
Z
'"<:lo
:;>,-
",,- o
t-I
:;:.8 . o
1""""1 1:- ~ 00 ~
lOOOI""""lO~~MOlO~lO CCCC~~M~~
[ ~~C?9~C?r:-~r:-C?9~9:t'
~ <:0,.....,
r;<:I Cl)'~"Cl 6M~M~OO~6oo~~oo~~~~~~~1O~6 OlOO<:OlC~lOC'1~t-OO"""'COM
:s0 ..c:",$
""-
~~Q '"
M~ Cl""'"
......
MI""""I~lO~M ~t-M~~
......
M~C'1: ~1""""I""""""I""'"IC'1l""""'1l""""1lOCC
Ul os;e
~
s.8
00 .... .~
"
03 Q ~
0 ... ..c: ;l
bO"" ....
Ul
r;<:I 'Of~
... ",0..
t-I ",..c: S
E-c
t-I S~$
...:I
t-I . '"
~..c:
P=l "'s+'
p -l,,1;l
...:I 1110 I=l
0
Ul .~
'" "cD:P
0
bO..c: :::I
.5B~O
~ ,DOW
"'"0"0
t-<",$
<' ..c:..c:
'" '" ...
CIl
t-<",z
..c:'"
.... 00
Appendix 867
--
0 0> 0 <:Q
I'-:"'?
";<00MI 1 I I l~~~
000 I 1~~:600!6~6
~CI':l~LOOC'1~U":lO';l
I: I
I I I I 1~66:C1:
MOO O"'l I I~
..;<
16
0.....
<COlO
..... C'l M
-
..;<
I 1 I I I I I I 0>0>
~~l 19':"'? I 000
'":~ ":l
I I~"'l I I I 1 I
100> 1 I .........
10M .10. . 10 ..... I I I: I I I I I MOO
0"'l I:
~-----
0 00 0 <C
1'-:"'";"
C'l'" I 1 I 1 I"?'?'?
0010 .... I l~~~~
.-I t-.-I C'l C'l a;.
~~
t- I I I: I: I I J~%%:~Z6~:;;
Mt- "'l M 16
0>
C'l 100>'" l.OC'l.....;-.:tt~~1""""4
..... ..;< 0":l(N1O,....,~
-------- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -
1O 1Ot- .... 1O 0 0
1
~1""""4 1""""4~~O~C1QO ooo~~ ~O~LO~~~~LO~LO~ool~~I~ ~~O';I
o~~66oo~~~~~~~~~6~~6~666~~~6~~~ MOO ~a;.66~
~~~~C'l~~ ~~M 1""""4~ 1""""4~~ ~C'1~ C'1 ~ ~ ~OI""""4~LO
C'l .-I 1""""4 1"""1
~LOM~._I~~I"""II"""I~I"""IC'1~~~~C'1~C1~~O';I~M~C1~C1~C1~LOOLOMI""""4I""""4MI""""4~
O~LO~~~OOI""""4C100~~lOLOLOC'100C'l1""""4000000~O';I00I""""40~OO~O';I00C1~~
~6~~~666oo6~~~~~oo~~~~~~M~oo6~~~~oooo~~~~6~oo~
C1~~C1~~OOOMI""""4~C1~~C'lM~~I"""I~M~LOI""""4MLO~OOOOMLO~~~.-IOO~C1~~
C'1~C1MC1~C1._1I"""1I""""4._1~ 1"""I.-IC'1I"""1C1.-1I"""1.-1.-1M.-I.-I1"""I C'1.-1 ~.-IC1 MC'lC'1
- - - - - ------ - - - - - - - - - - - - - - - - - - - - - - - - - - - - 1
*
868 Quantitative Inorganic Analysi8
12 C. 25 C. [ 38 C.
I I
pH. pH. pH.
CH 3 COOH (O'OIN), CH 3 COONa (OOIN) . 4710 4700 4710
CH 3 COOH (O'lN), CH 3 COONa (OIN) 4650 4640 4'635
Potassium acid phthalate (005M). . . 4000 4000 4015
Potassium acid tartrate (003M) (D. 1. Hitchcock
and A. C. Taylor, 1937) - 3567 -
t See also E. R. Smith and R. G. Bates, " Standards for pH Determinations", Oomptes
Rendus de la Quinzieme Oonference, International Union of Pure and Applied Chemistry,
Amsterdam, 1949.
Appendix 869
2. pH Range: 065-520; 18 C. (Walpole, 1914)
X (ml.) Y (ml.)
Citric acid_
pH_ X (ml.)
Na 2HP0 4
Y (ml.)
Citric acid.
I pH.
Na 2HP0 4 -
040 1960 22 1072 928 52
124 1876 24 1115 8'S5 54
21S 17S2 26 1160 840 56
317 16S3 28 1209 791 58
411 15'S9 30 1263 737 60
494 1506 32 1322 67S 62
570 1430 34 1385 615 64
644 1356 36 1455 545 66
710 1290 38 1545 455 68
771 1229 4'0 1647 353 70
828 1172 42 1739 261 72
S'82 111S 44 lS17 l'S3 74
935 1065 46 lS73 127 76
986 1014 48 1915 0S5 78
1030 970 50 1945 055 80
\
870 Quantitative Inorganic Analysis
5. pH Range: 529-804; 18 C. (Sorensen, 1909-1Z)
I I NaX HP0
X (ml.) Y (mI.)
Ka 2 HP0 41 KH 2PO .
025 975
I pH.
529
(mI.)
2
50
4
Y (ml.)
KH 2P0 4-
50
pH.
681
05 95 559 60 40 698
10 90 591 70 30 717
20 80 624 80 20 738
30 70 647 I 90 10 773
40 60 664 95 05 804
I
6. pH Ranges: 22-38,40-62,58-80, 7B-100; 20 C.
(Clark and Lubs, 1916)
...
(A) pH 22-38. 50 Ml. OZM-KHphthalate + P ml_ OZM-HCl, diluted
to ZOO ml.
(B) pH 40--62_ 50 Ml. OZM-KH phthalate + Q ml. OZM-NaOH,
diluted to 200 ml.
(0) pH 58-80. 50 Ml. 02M-KH 2 P0 4 + R ml. 02M-NaOH, diluted
to ZOO ml.
(D) pH 78-100. 50 Ml. 0ZM-H 3 BO a and 02M-KCl * + S ml. OZM-
NaOH, diluted to 200 ml.
A. B. o. D.
X (ml.)
Na salt.
\ Y (ml.)
HeI.
I pH.
I X (ml.)
Na salt.
I Y (ml.)
HeI.
I
I pH.
522 478 680 823 177 840
536 464 700 871 129 860
554 446 720 908 092 880
581 419 740 936 064 900
615 385 760 952 048 920
662 338 780 974 026 940
716 284 800 985 015 960
Appendix 871
8. pH Range: 845-12,,; 24 C. (Sorensen-Walbum, 1920)
--
10-Ml. mixtures of X ml. of OIM-glycine + OIM-NaCI * and Y ml. of
OIM-NaOH.
9. pH Ranges: 140-220,230-330,290-410,340-520,480-620;
25 C. (German imd Vogel, 1937)
Y (ml.).
X (ml.).
I I pH.
II X (ml.).
I Y (ml.).
I- - -pH.- - -
500 00 230 124 376 290
442 58 240 100 400 300
358 142 250 80 420 310
276 224 260 62 438 320
212 288 270 50 450 330
185 315 280
X (ml.).
I
Y (ml.). pH.
I X (ml.).
I Y (ml.).
I pH.
452 48 290 i 148 352 360
396 104 300 123 377 370
340 160 310 101 399 380
284 216 320 84 416 390
24'8 252 330 67 433 400
214 286 340 54 446 410
180
I
320 350 I I
872 Quantitative Inorganic Analysis
UNITS OF LENGTH
I millimetre (mm.) = 003937 inch. I inch (in.) = 25400 millimetres.
I centimetre (cm.) = 03937 inch. I inch = 25400 centimetres.
I metre (m.) = 39370 inches. I foot (ft.) = 304801 millimetres.
I metre = 32808 feet. 1 foot = 030480 metre.
I milometre (km.) = 109361 yards. I yard (yd.) = 091440 metre.
I kilometre = 062137 mile. I mile = 160934 metres.
UNITS OF AREA
I square mm. = 0001550 sq. in. I square in. = 64516 sq. mm.
I square cm. = 01550 sq. in. I square in. = 64516 sq. cm.
I square metre = 15500 sq. ins. I square ft. = 92903 sq. cm.
I square metre = 107638 sq. ft. I square ft. = 09290 sq. m.
1 square metre = 11960 sq. yds. I square yd. = 083613 sq. ITL
I square km. = 038610 sq. mile. I acre = 040469 hectare.
I hectare = 24710 acres. I square mile = 25900 sq. km.
UNITS OF VOLUME
I cubic mm. = 000006102 cubic in. I cubic in. = 16,387 cubic mm.
I cubic cm. (c.c. or mI.) I cubic in. = 16387 mI.
= 0061024 cubic in. I cubic ft. = 0028317 cubic m.
I cubic m. = 61,024 cubic ins. 1 cubic ft. = 28317 litres.
I cubic m. = 353144 cubic ft. I cubic yd. = 07645 cubic m.
= 13079 cubic yds.
MEASURES OF LIQUID CAPACITY
Imperial or British Units
1 gill 14206 m!. I litre = 70392 gills.
1 pint = 4 gills 56825 mI. = 17598 pints.
1 quart = 2 pints = 113649 litres. = 08'8000 quart.
1 gallon = 4 quarts = 4'54596 litres. I = 022000 gallon.
874 Quantitative Inorganic Analysis
Apothecaries' Units (British)
1 minim = 0059192 ml.
1 fluid scruple = 20 minims = 11838 ml.
1 fluid drachm = 3 scruples = 35515 rul.
I fluid ounce = 8 fluid drachms = 28412 rul.
I pint = 20 fluid ounces = 56825 rul.
I gallon = 8 pints = 454596 litres.
I litre = 168941 minims.
= 28157 fluid drachms.
= 35196 fluid ounces.
U.s. Units
I gill 118292 ml. I litre = 84537 gills.
I pint = 4 gills 473167 ml. = 21134 pints.
I quart = 2 pints 094633 litre. = 026418 gallon.
I gallon = 4 quarts = 378533 litres.
UNITS OF MASS
A voirdupois Weight
1 grain =
64799 mg.
1 dram = 273437 grains = 177185 g. ,
1 ounce = 16 drams = 4375 grains = 2834954 g.
I pound = 16 ounces = 7000 grains = 4535926 g.
1 stone = 14 pounds = 635030 kg.
1 quarter = 28 pounds = 1270059 kg.
I hundredweight = 112 pounds = 5080238 kg.
I gram = 154325 grains.
I decagram = 10 grams = 564383 drams.
1 hectogram = 100 grams = 352739 ounces.
I kilogram = 1000 grams = 2204621 pounds.
1 myriagram = 10 kilograms = 2204621 pounds.
1 quintal = 100 kilograms = 198641 hundredweigh~8
1 millier = I metric ton = 1000 kilograms = 09842059 ton.
Troy Weight
I grain = 64799 mg.
I carat = 4 grains = 025920 g.
I pennyweight (dwt.) = 6 carats = 24 grains = 129598 g.
I ounce = 20 pennyweights = 480 grains = 311035 g.
I pound = 12 ounces = 5760 grains = 3732418 g.
1 gram = 154323 grains.
= 3858 carats.
= 0643 pennyweights.
= 003215 ounce.
Appendix 875
Apothecaries' Weight
1 grain = 64799 mg.
1 scruple = 20 grains = 129598 g ..
1 drachm = 3 scruples = 388794 g.
1 ounce = 8 drachms = 480 grains = 311035 g.
1 pound = 12 ounces = 3732418 g.
1 gram = 154323 grains.
= 07716 scruples.
= 02572 drachms.
= 003215 ounce.
A a Alpha a N v Nu n
B fl Beta b 8 g Xi x
r y Gamma g 0 0 Omicron 6
Delta II
A d I Pi
,"
tr
P
E Epsilon e P p Rho r
Z Zeta z ~ (J Sigma s
\ T
H ." Eta Ii r Tau t
0 IJ Theta th Y v Upsilon u
I L Iota i <I> f Phi ph
K K Kappa k X X Chi ch
A ,\ Lambda 1 ' .(1 Psi ps
n
I M I" , Mu m
I, I '" Omega 6
I
876 Quantitative Inorganic Analysis
Precipitation Reactions
Use of Standard Solutions of Silver Nitrate and of Ammonium Thiocyanate
(i) Preparation of approx. OIN-silver nitrate solution (Section 111, 22;
Procedure B).
(ii) Standardisation of the silver nitrate solution with standard sodium
chloride solution: (a) using potassium chromate as indicator-Mohr's method /
, VOLUMETRIC ANALYSIS
Acidimetry and Alkalimetry
(i) Calibration of weights (Section II, 8).
(ii) Calibration of volumetric apparatus:
(a) volumetric flasks, 250-ml., 500-ml., lOOO-ml. (Section II, 20) ;
(b) pipettes, lO-ml., 25-ml., 50-ml. (Section II, 21);
(c) burette (Section II, 22).
(iii) Preparation of OlN-hydrochloric acid (Section III, 3 OJ; III, 4).
Standardisation against:
(a) borax (Section III, 4B) ;
(b) anhydrous sodium carbonate (Section III, 4A).
(iv) Preparation of OlN-sodium hydroxide (Section III, 5; Procedure A).
Standardisation with:
(a) OlN-hydrochloric acid (Section III, 6; Procedure A);
(b) A.R. potassium hydrogen phthalate (Section III, 6; Procedure B).
(v) Determination of strength of glacial acetic acid (Section III, 10).
(vi) Determination of NH3 in an ammonium salt (Section III, 18; direct
method) or of NaN0 3 in Chili saltpetre (Section III, 19).
(vii) Determination of nitrogen by Kjeldahl's method (Section III, 20).
(viii) Determination of nickel with dicyandiamidine sulphate (Section
IV,32D).
PreCipitation and Complex-formation Reactions
(i) Preparation and standardisation of OlN (or of O05N) silver nitrate
(Section III, 22 and Section III, 23A and B).
(ii) Determination of chlorine in A.R. barium chloride dihydrate (Section
III,24).
(iii) Determination of bromine in A.R. potassium bromide (Section III, 25;
eosin indicator).
(iv) Determination of iodine in A.R. potassium iodide (Section III, 26; I'.
di -iododimethylfluorescein indicator).
(v) Determination of chloride and iodide in admixture (~ection III, 29A).
Appendix 879
(vi) Preparation and standardisation of OlN-ammonium thiocyanate
(Section III, 31).
(vii) Determination of bromine in A.R. potassium bromide (Section 111,34;
Volhard's method).
(viii) Determination of chlorate in A.R. potassium chlorate.
Note. Reduce the chlorate with ferrous sulphate solution, Section IV, 58, add
an excess (measured volume) of O'lN-silver nitrate, and coagulate the silver
chloride by warming and stirring. Cool, filter, and titrate the filtrate and wash-
ings with standard O'lN -ammonium thiocyanate using ferric alum as indicator,
and thus determine the excess of O'lN -silver nitrate.
AMPEROMETRIC TITRATIONS
(i) Determination of lead with standard potassium dichromate solution
(Section IX, 3).
(ii) Determination of sulphate with standard lead nitrate solution (Section
IX, 4).
(iii) Determination of nickel with dimethylglyoxime (Section IX, 5).
GAS ANALYSIS
(i) *Determination of oxygen in the air (Section X, 9).
(ii) Analysis of coal gas with the Bunte burette (Section X, 6B).
(iii) *Analysis of coal gas with the Orsat apparatus (Section X, 6C).
(iv) Analysis of coal gas with the Ambler apparatus (Section X, 6D).
(v) Determination of a nitrate with the Lunge nitrometer (Section X, 11).
(vi) *Determination of hydrogen peroxide (Section X, 12).
(vii) *Evaluation of pyrolusite (Section X, 13).
(viii) Evaluation of zinc dust (Section X, 15).
(ix) Determination of ammonia in an ammonium salt (Section X, 16).
Appendix 883
Quantities Re-
quiredfor 1
Litre of
Saturated
Specific Solution.
Reagent. Formula. Gravity_ Molarity.
Grams Ml. of
"
of Re-
agent. Water.
I I II :1 :II;i:i:I~SI
A
0 1 I 2 I 3 I 4 5 6 I '(
I 8 I 9 11!:I 0
10 0000 0043\ 0086 0128 0170 0212 0253 0294 0334 0374 4 8 12 1721 25\29!33 37
11 0414 0453 0492 0531 0569 0607 0645 0682 0719 0755 4 811 1519 232630 34
12 0792 0828 0864 0899 0934 0969 1004 1038 1072 1106 3 7 10 1417 2124 2831
13 1139 1173 1206 1239 1271 1303 1335 1367 1399 1430 3 6 10 13 16 1923 2629
14 1461 1492 1 1523 1553 1584 1614 1644 1673 1703 1732 3 6 912 15 18 2124 27
15 1761 1790 1818 1847 1875 1903 1931 1959 1987 2014 3 6 811 1417 2022 25
16 2041 2068 2095 2122 2148 2175 2201 2227 2253 2279 3 5 811 13 16 1821 24
17 2304 2330 2355 2380 2405 2430 2455 2480 2504 2529 2 5 710 12 15 1720 22
18 2553 2577 2601 2625 2648 2672 2695 2718 2742 2765 2 5 7 9 1214 1619 21
19 2788 2810 2833 2856 2878 2900 2923 2945 2967 2989 2 4 7 9 11 13 1618 20
20 3010 3032 3054 3075 3096 3118 3139 3160 3181 3201 2 4 6 811 1315 1719
21 3222 3243 3263 3284 3304 3324 3345 3365 3385 3404 2 4 6 810 1214 1618
22 3424 3444 3464 3483 3502 3522 3541 3560 3579 3598 2 4 6 810 1214 1517
23 3617 3636 3655 3674 3692 3711 3729 3747 3766 3784 2 4 6 7 9 1113 1517
24 3802 3820 3838 3856 3874 3892 3909 3927 3945 3962 2 4 5 7 9 1112 1416
25 3979 3997 4014 4031 4048 4065 4082 4099 4116 4133 2 3 5 7 910 1214 15
26 4150 4166 4183 4200 4216 4232 4249 4265 4281 4298 2 3 5 7 810 1113 15
27 4314 4330 4346 4362 4378 4393 4409 4425 4440 4456 2 3 5 6 8 9 1113 14
28 4472 4487 4502 4518 4533 4548 4564 4579 4594 4609 2 3 5 6 8 9 1112 14
29 4624 4639 4654 4669 4683 4698 4713 4728 4742 4757 1 3 4 6 7 9 1012 13
30 4771 4786 4800 4814 4829 4843 4857 4871 4886 4900 1 3 4 6 7 910 1113
31 4914 4928 4942 4955 4969 4983 4997 5011 5024 5038 1 3 4 6 7 810 11 12
32 5051 5065 5079 5092 5105 5119 5132 5145 5159 5172 1 3 4 5 7 8 9 1112
33 5185 5198 5211 5224 5237 5250 5263 5276 5289 5302 1 3 4 5 6 8 9 1012
34 5315 5328 5340 5353 5366 5378 5391 5403 5416 5428 1 3 4 5 6 8 9 1011
355441 5453 5465 5478 5490 5502 5514 5527 5539 5551
1 2 4 5 6 7 910 11
365563 5575 5587 5599 5611 5623 5635 5647 5658 5670
1 .2 4 5 6 7 810 11
375682 5694 5705 5717 5729 5740 5752 5763 5775 5786
1 2 3 5 6 7 8 9 10
385798 5809 5821 5832 5843 5855 5866 5877 5888 5899
1 2 3 5 6 7 8 9 10
39 5911 5922 5933 5944 5955 5966 5977 5988 5999 6010 1 2 3 4 5 7 8 9 10
40 6021 6031 6042 6053 6064 6075 6085 6096 6107 6117 1 2 3 4 5 6 8 910
41 6128 6138 6149 6160 6170 6180 6191 6201 6212 6222 1 2 3 4 5 6 7 8 9
42 6232 6243 6253 6263 6274 6284 6294 6304 6314 6325 1 2 3 4 5 6 7 8 9
43 6335 6345 6355 6365 6375 6385 6395 6405 6415 6425 1 2 3 4 5 6 7 8 9
44 6435 6444 6454 6464 6474 6484 6493 6503 6513 6522 1 2 3 4 5 6 7 8 9
45 6532 6542 6551 6561 6571 6580 6590 6599 6609 6618 1 2 3 4 5 6 7 8 9
46 6628 6637 6646 6656 6665 6675 6684 6693 6702 6712 1 2 3 4 5 6 7 7 8
47 6721 6730 6739 6749 6758 6767 6776 6785 6794 6803 1 2 3 4 5 5 6 7 8
48 6812 6821 6830 6839 6848 6857 6866 6875 6884 6893 1 2 3 4 5 5 6 7 8
49 6902 6911 6920 6928 6937 6946 6955 6964 6972 6981 1 2 3 4 4 5 6 7 8
50 6990 6998 7007 7016 7024 7033 7042 7050 7059 7067 1 2 3 3 4 5 6 7 8
51 7076 7084 7093 7101 7110 7118 7126 7135 7143 7152 1 2 3 3 4 5 6 7
8
52 7160 7168 7177 7185 7193 7202 7210 7218 7226 7235 1 2 2 3 4 5 6 7
7
53 7243 7251 7259 7267 7275 7284 7292 7300 7308 7316 1 2 2 3 4 5 6 6
7
54 7324 7332 7340 7348 7356 7364 7372 7380 7388 7396 1 2 2 3 4 5 6 6 7
I 0 I 1 I 2 I 3 I 4
1 5 6 I 7 8 1 9 11 2 13 14 15 61 7 18 19
FOUR-FIGURE LOGARITHMS 885
55
II0
7404
1 I 2
7412 7419
3 I 4
7427 7435
I I
5
7443
6
7451
I 7 I 8
7459 7466
9
7474 1
MEAN DIFFERENCES
11213141516171819
2 2 3 4 5 5 6 7
56 7482 7490 7497 7505 7513 7520 7528 7536 7543 7551 1 2 2 3 4 5 5 6 7
57 7559 7566 7574 7582 7589 7597 7604 7612 7619 7627 1 2 2 3 4 5 5 6 7
58 7634 7642 7649 7657 7664 7672 7679 7686 7694 7701 1 1 2 3 4 4 5 6 7
59 7709 7716
.
7723 7731 7738 7745 7752 7760 7767 7774 1 1 2 3 4 4 5 6 7
60 7782 7789 7796 7803 7810 7818 7825 7832 7839 7846 1 1 2 3 4 4 5 6 6
61 7853 7860 7868 7875 7882 7889 7896 7903 7910 7917 I 1 2 3 4 4 5 6 6
62 7924 7931 7938 7945 7952 7959 7966 7973 7980 7987 1 1 2 3 3 4 5 6 6
63 7993 8000 8007 8014 8021 8028 8035 8041 8048 8055 1 1 2 3 3 4 5 5 6
64 8062 8069 8075 8082 8089 8096 8102 8109 8116 8122 1 1 2 3 3 4 5 5 6
65 8129 8136 8142 8149 8156 8162 8169 8176 8182 8189 1 1 2 3 3 4 5 5 6
66 8195 8202 8209 8215 8222 8228 8235 8241 8248 8254 1 1 2 3 3 4 5 5 6
67 8261 8267 8274 8280 8287 8293 8299 8306 8312 8319 1 1 2 3 3 4 5 5 6
68 8325 8331 8338 8344 8351 8357 8363 8370 8376 8382 1 1 2 3 3 4 4 5 6
69 8388 8395 8401 8407 8414 8420 8426 8432 8439 8445 1 1 2 2 3 4 4 5 6
70 8451 8457 8463 8470 8476 8482 8488 8494 8500 8506 1 1 2 2 3 4 4 5 6
71 8513 8519 8525 8531 8537 8543 8549 8555 8561 8567 1 1 2 2 3 4 4 5 5
72 8573 8579 8585 8591 8597 8603 8609 8615 8621 8627 1 1 2 2 3 4 4 5 5
73 8633 8639 8645 8651 8657 8663 8669 8675 8681 8686 1 1 2 2 3 4 4 5 5
74 8692 8698 8704 8710 8716 8722 8727 8733 8739 8745 1 1 2 2 3 4 4 5 5
75 8751 8756 8762 8768 8774 8779 8785 8791 8797 8802 1 1 2 2 3 3 4 5 5
76 8808 8814 8820 8825 8831 8837 8842 8848 8854 8859 1 1 2 2 3 3 4 5 5
77 8865 8871 8876 8882 8887 8893 8899 8904 8910 8915 1 1 2 2 3 3 4 4 5
78 8921 8927 8932 8938 8943 8949 8954 8960 8965 8971 1 1 2 2 3 3 4 4 5
79 8976 8982 8987 8993 8998 9004 9009 9015 9020 9025 1 1 2 2 3 3 4 4 5
80 9031 9036 9042 9047 9053 9058 9063 9069 9074 9079 1 1 2 2 3 3 4 4 5
81 9085 9090 9096 9101 9106 9112 9117 9122 9128 9133 1 1 2 2 3 3 4 4 5
82 9138 9143 9149 9154 9159 9165 9170 9175 9180 9186 1 1 2 2 3 3 4 4 5
83 9191 9196 9201 9206 9212 9217 9222 9227 9232 9238 1 1 2 2 3 3 4 4 5
84 9243 9248 9253 9258 9263 9269 9274 9279 9284 9289 1 1 2 2 3 3 4 4 5
85 9294 9299 9304 9309 9315 9320 9325 9330 9335 9340 1 1 2 2 3 3 4 4 5
86 9345 9350 9355 9360 9365 9370 9375 9380 9385 9390 1 1 2 2 3 3 4 4 5
87 9395 9400 9405 9410 9415 9420 9425 9430 9435 9440 0 1 1 2 2 3 3 4 4
88 9445 9450 9455 9460 9465 9469 9474 9479 9484 9489 0 1 1 2 2 3 3 4 4
89 9494 9499 9504 9509 9513 9518 9523 9528 9533 9538 0 1 1 2 2 3 3 4 4
90 9542 9547 9552 9557 9562 9566 9571 9576 9581 9586 0 1 1 2 2 3 3 4 4
91 9590 9595 9600 9605 9609 9614 9619 9624 9628 9633 0 1 1 2 2 3 3 4 4
92 9638 9643 9647 9652 9657 9661 9666 9671 9675 9680 0 1 1 2 2 3 3 4 4
93 9685 9689 9694 9699 9703 9708 9713 9717 9722 9727 0 1 1 2 2 3 3 4 4
94 9731 9736 9741 9745 9750 9754 9759 9763 9768 9773 0 1 1 2 2 3 3 4 4
95 9777 9782 9786 9791 9795 9800 9805 9809 9814 9818 0 1 1 2 2 3 3 4 4
96 9823 9827 9832 9836 9841 9845 9850 9854 9859 9863 0 1 1 2 2 3 3 4 4
97 9868 9872 9877 9881 9886 9890 9894 9899 9903 9908 0 1 1 2 2 3 3 4 4
98 9912 9917 9921 9926 9930 9934 9939 9943 9948 9952 0 1 1 2 2 3 3 4 4
99 9956 9961 9965 9969 9974 9978 9983 9987 9991 9996 0 1 1 2 2 3 3 3 4
1 0 1 1 1 2 1 3 1 4 1 5 1 6 1 7 1 8 1 9 111213141 5 6 171819 i
FIVE-FIGURE LOGARITHMS * .
* The five-figure logarithm tables (but in a modified set-out) are taken from E. Hope, The
Chemists' Year Book, 1939, and are reproduced by kind permission of the publishers, Messrs.
Sherratt and Hughes, Timperley, Cheshire, England. Permission to reproduce five-figure
logarithm tables was also kindly granted by Messrs. G. Bell and Sons Ltd., Portugal Street,
London, W.C.2, England, from their Synopsis of Applicable Mathematics by L. Silberstein, and
also by Dr. A. Lange from his Handbook of Chemistry, 2nd Edition, 1937 (Handbook Publishers
Inc., Sandusky, Ohio, U.S.A.).
FIVE-FIGURE LOGARITHMS: 100--150 887
- I 0 1 2 3 4 I 5 I 6 7 8 9
PROPORTIONAL PARTS
1 2 3 4 I 5 I 6 7 8 9
100 00 000 043 087 130 173 217 260 303 346 389 4 8 13 17 J 21 26 30 35 39
101 432 475 518 561 604 647 689 732 775 817 4 8 13 17 21 26 30 34 39
102 860 903 945 988 030 072 115 157 199 242 4 8 13 17 21 25 30 34 38
103 01 284 326 368 410 452 494 536 578 620 662 4 8 13 17 21 25 30 34 38
104 703 745 787 828 870 912 953 995 036 078 4 8 12 17 21 25 29 34 38
105 02 119 160 202 243 284 325 366 407 449 490 4 8 12 17 21 25 29 33 37
106 531 572 612 653 694 735 776 816 857 898 4 8 12 16 20 24 29 33 37
107 938 979 019 060 100 141 181 222 262 302 4 8 12 16 20 24 28 32 36
108 03 342 383 423 463 503 543 583 623 663 703 4 8 12 16 20 24 28 32 36
109 743 782 822 862 902 941 981 021 060 100 4 8 12 16 20 24 28 32 36
110 04 139 179 218 258 297 336 376 415 454 493 4 8 12 16 20 24 27 31 35
111 532 571 610 650 689 727 766 805 844 883 4 8 12 16 20 23 27 31 35
112 922 961 999 038 077 115 154 192 231 269 4 8 12 16 20 23 27 31 35
113 05 308 346 385 423 461 .')00 538 576 614 652 4 8 11 15 19 23 27 30 34
114 690 729 767 805 843 881 918 956 994 032 4 8 II 15 19 23 26 30 34
115 06 070 108 145 183 221 258 296 333 371 408 4 8Il 15 19 23 26 30 34
116 446 483 521 558 595 633 670 707 744 781 4 7 II 15 19 22 26 30 33
117 819 856 893 930 967 004 041 078 115 151 4 7 11 15 19 22 25 29 33
118 07 188 225 262 298 335 372 403 445 482 518 4 7 11 15 18 22 25 29 33
119 555 591 628 664 700 737 773 809 846 882 4 7 11 15 18 22 25 29 32
120 918 954 990 027 063 099 135 171 207 243 4 7 11 14 18 22 25 29 32
121 08 279 314 350 386 422 458 493 529 565 600 4 7 11 14 18 21 25 29 32
122 636 672 707 743 778 814 849 884 920 955 4 7 11 14 18 21 25 28 32
123 991 025 061 096 132 167 202 237 272 307 4 7 11 14 18 21 25 28 32
124 09 342 377 412 447 482 517 552 587 621 656 3 7 10 14 18 21 24 28 31
125 691 726 760 795 830 864 899 934 968 003 3 7 10 14 17 21 24 28 31
126 10 037 072 106 140 175 209 243 278 312 346 3 7 10 14 17 21 24 27 31
127 380 415 449 483 517 551 585 619 653 687 3 7 10 14 17 20 24 27 31
128 721 755 789 823 856 890 924 958 992 025 3 7 10 14 17 20 24 27 30
129 11 059 093 126 160 193 227 260 294 327 361 3 7 10 13 17 20 24 27 30
130 394 428 461 494 528 561 594 628 661 694 3 7 10 13 17 20 23 27 30
131 727 760 793 826 860 893 926 959 992 024 3 7 10 13 17 20 23 26 30
132 12 057 090 123 156 189 222 254 287 320 352 3 7 10 13 16 20 23 26 29
133 385 418 450 483 516 548 581 613 646 678 3 6 10 13 16 20 23 26 29
134 710 743 775 808 840 872 905 937 969 001 3 6 10 13 16 19 23 26 29
135 13 033 066 098 130 162 194 226 258 290 322 3 6 10 13 16 19 22 26 29
136 354 386 418 450 481 513 545 577 609 640 3 6 10 13 16 19 22 25 29
137 672 704 735 767 799 830 862 893 925 956 3 6 10 13 16 19 22 25 28
138 988 019 051 082 114 145 176 208 239 270 3 6 9 13 16 19 22 25 28
139 14 301 333 364 395 426 457 489 520 551 582 3 6 9 12 16 19 22 25 28
140 613 644 675 706 737 768 799 829 860 891 3 6 9 12 15 19 22 25 28
141 922 953 983 014 045 076 106 137 168 198 3 6 9 12 15 18 21 25 28
142 15 229 259 290 320 351 381 412 442 473 503 3 6 9 12 15 18 21 24 27
143 534 564 594 625 655 685 715 746 776 806 3 6 9 12 15 18 21 24 27
144 836 866 897 927 957 987 017 047 077 107 3 6 9 12 15 18 21 24 27
145 16 137 167 197 227 256 286 316 346 376 406 3 6 9 12 15 18 21 24 27
146 435 465 495 524 554 584 613 643 673 702 3 6 9 12 15 18 21 24 27
147 732 761 791 820 850 879 909 938 967 997 3 6 9 12 15 18 21 24 26
148 17 026 056 085 114 143 173 202 231 260 289 3 6 9 12 15 18 20 23 26
149 319 348 377 406 435 464 493 522 551 580 3 6 9 12 15 17 20 23 26
150 609 638 667 696 725 754 782 811 840 869 3 6 9 12 14 17 20 23 26
0 1 2 3 4 I 5 I 6 7 8 9 1 2 3 4 I 5 I 6 7 8 9
00 000-17 869
888 FIVE-FIGURE LOGARITHMS : 150~200
150
0
17 609
1
638
2
667
3
696
4
725
5 I 6
754
7 8
782 811 840 869
9 I1 2 3 4
3 6
PROPORTIONAL PARTS
9 12
I 5
14
I 6 7 8 9
17 20 23 26
151 898 926 955 984 013 041 070 099 127 156 3 6 9 11 14 17 20 23 26
152 18 184 213 241 270 298 327 355 384 412 441 3 6 9 11 14 17 20 23 25
153 469 498 526 554 583 611 639 667 696 724 3 6 9 11 14 17 20 23 25
154 752 780 808 837 865 893 921 949 977 005 3 6 8 11 14 17 20 23 25
155 19 033 061 089 117 145 173 201 229 257 285 3 6 8 11 14 17 20 22 25
156 312 340 368 396 424 451 479 507 535 562 3 6 8 11 14 17 20 22 25
157 590 618 645 673 700 728 756 783 811 838 3 5 8 11 14 17 19 22 25
158 866 893 921 948 976 003 030 058 085 112 3 5 8 11 14 16 19 22 25
159 20 140 167 194 222 249 276 303 330 358 385 3 5 8 11 14 16 19 22 25
160 412 439 466 493 520 547 575 602 629 656 3 5 8 11 14 16 19 22 24
161 683 710 736 763 790 817 844 871 898 925 3 5 8 II 13 16 19 22 24
162 951 978 005 032 059 085 112 139 165 192 3 5 8 11 13 16 19 21 24
163 21 219 245 272 299 325 352 378 405 431 457 3 5 8 11 13 16 19 21 24
164 484 511 537 564 590 617 643 669 696 722 3 5 8 11 13 16 18 21 24
165 748 775 801 827 854 880 906 932 958 985 3 5 8 10 13 16 18 21 24
166 22 011 037 063 089 115 141 167 194 220 246 3 5 8 10 13 16 18 21 23
167 272 298 324 350 376 401 427 453 479 505 3 5 8 10 13 16 18 21 23
168 531 557 583 608 634 660 686 712 737 763 3 5 8 10 13 15 18 21 23
169 789 814 840 866 891 917 943 968 994 019 3 5 8 10 13 15 18 21 23
170 23 045 070 096 121 147 172 198 223 249 274 3 5 8 10 13 15 18 20 23
171 300 325 350 376 401 426 452 477 502 528 3 5 8 10 13 15 18 20 23
172 553 578 603 629 654 679 704 729 754 779 3 5 8 10 13 15 18 20 23
173 805 830 855 880 905 930 955 980 005 030 2 5 7 10 13 15 18 20 23
174 24 055 080 105 130 155 180 204 229 254 279 2 5 7 10 12 15 17 20 22
175 304 329 353 378 403 428 452 477 502 527 2 5 7 10 12 15 17 20 22
176 551 576 601 625 650 674 699 724 748 773 2 5 7 10 12 15 17 20 22
177 797 822 846 871 895 920 944 969 993 018 2 5 7 10 12 15 17 20 22
178 25 042 066 091 115 139 164 188 212 237 261 2 5 7 10 12 15 17 19 22
179 285 310 334 358 382 406 431 455 479 503 2 5 7 10 12 15 17 19 22
180 527 551 575 600 624 648 672 696 720 744 2 5 7 10 12 14 17 19 22
181 768 792 816 840 864 888 912 935 959 983 2 5 7 10 12 14 17 19 22
182 26 007 031 055 079 102 126 150 174 198 221 2 5 7 10 12 14 17 19 21
183 245 269 293 316 340 364 387 411 435 458 2 5 7 10 12 14 17 19 21
184 482 505 529 553 576 600 623 647 670 694 2 5 7 9 12 14 17 19 21
185 717 741 764 788 811 834 858 881 905 928 2 5 7 9 12 14 16 19 21
186 951 975 998 021 045 068 091 114 138 161 2 5 7 9 12 14 16 19 21
187 27 184 207 231 254 277 300 323 346 370 393 2 5 7 9 12 14 16 19 21
188 416 439 462 485 508 531 554 577 600 623 2 5 7 9 12 14 16 18 21
189 646 669 692 715 738 761 784 807 829 852 2 5 7 9 11 14 16 18 21
190 875 898 921 944 967 989 012 035 058 081 2 5 7 9 II 14 16 18 21
191 28 103 126 149 171 194 217 240 262 285 307 2 5 7 9 11 14 16 18 20
192 330 353 375 398 420 443 466 488 510 533 2 5 7 9 II 14 16 18 20
193 556 578 601 623 646 668 691 713 735 758 2 4 7 9 II 13 16 18 20
194 780 803 825 847 870 892 914 937 959 981 2 4 7 9 11 13 16 18 20
195 29 003 026 048 070 092 115 137 159 181 203 2 4 7 9 11 13 16 18 20
196 226 248 270 292 314 336 358 380 403 425 2 4 7 9 11 13 15 18 20
197 447 469 491 513 535 557 579 601 623 645 2 4 7 9 11 13 15 18 20
198 667 688 710 732 754 776 798 820 842 863 2 4 7 9 II 13 15 18 20
199 885 907 929 951 973 994 I 016 038 060 081 2 4 7 9 11 13 15 17 20
200 30 103 125 146 168 190 211 i 233 255 276 298 2 4 7 9 11 13 15 17 20
0 1 2 3 4 I 5 I
6 7 8 9 I1 2 3 4 I 5 I
6 7 8 9
'17 609~'30 298
FIVE-FIGURE LOGARITHMS: 200-250 889
-r-
I I PROPORTIONAL PARTS
0 1 2 3 4 I 5 I 6 7 8 9 11 2 3 4 I 5 I 6 7 8 9
200 30 103 125 146 168 190 21I 233 255 276 298 2 4 7 9 II 13 15 17 20
201 320 341 363 384 406 428 449 471 492 514 2 4 6 9 II 13 15 17 19
202 535 557 578 600 621 642 664 685 707 728 2 4 6 9 11 13 15 17 19
203 750 771 792 814 835 856 877 899 920 942 2 4 6 9 11 13 15 17 19
204 963 984 006 027 048 069 091 112 133 154 2 4 6 8 II 13 15 17 19
205 31 175 197 218 239 260 281 302 323 345 366 2 4 6 8 11 13 15 17 19
206 387 408 429 450 471 492 513 534 555 576 2 4 6 8 11 13 15 17 19
207 597 618 639 660 681 702 723 744 765 785 2 4 6 8 10 13 15 17 19
208 806 827 848 869 890 91I 931 952 973 994 2 4 6 8 10 13 15 17 19
209 32 015 035 056 077 098 1I8 139 160 181 201 2 4 6 8 10 12 15 17 19
210 222 243 263 284 305 325 346 366 387 408 2 4 6 8 10 12 14 16 18
211 428 449 469 490 510 531 552 572 593 613 2 4 6 8 10 12 14 16 18
212 634 654 675 695 715 736 756 777 797 818 2 4 6 8 10 12 14 16 18
213 838 858 879 899 919 940 960 980 001 021 2 4 6 8 10 12 14 16 18
214 33 041 062 082 102 122 143 163 183 203 224 2 4 6 8 10 12 14 16 18
215 244 264 284 304 325 345 365 385 405 425 2 4 6 8 10 12 14 16 18
216 445 465 486 506 526 546 566 586 606 626 2 4 6 8 10 12 14 16 18
217 646 666 686 706 726 746 766 786 806 826 2 4 6 8 10 12 14 16 18
218 846 866 885 905 925 945 965 985 005 025 2 4 6 8 10 12 14 16 18
219 34 044 064 084 104 124 143 163 183 203 223 2 4 6 8 10 12 14 16 18
220 242 262 282 301 321 341 361 381 400 420 2 4 6 8 10 12 14 16 18
221 '439 459 479 498 518 537 557 577 596 616 2 4 6 8 10 12 14 16 18
222 635 655 674 694 713 733 753 772 792 81I 2 4 6 8 10 12 14 16 18
223 830 850 869 889 908 928 947 966 986 005 2 4 6 8 10 12 14 16 18
224 35 025 044 064 083 102 122 141 160 180 199 2 4 6 8 10 12 14 15 17
225 218 238 257 276 295 315 334 353 372 392 2 4 6 8 10 12 14 15 17
226 411 430 449 468 488 507 526 545 564 583 2 4 6 8 10 12 13 15 17
227 603 622 641 660 679 698 717 736 755 774 2 4 6 8 10 11 13 15 17
228 793 813 832 851 870 889 908 927 946 965 2 4 6 8 10 11 13 15 17
229 984 003 021 040 059 078 097 116 135 154 2 4 6 8 9 11 13 15 17
230 36 173 192 211 229 248 267 286 305 324 342 2 4 6 8 9 11 13 15 17
231 361 380 399 418 437 455 474 493 511 530 2 4 6 8 9 11 13 15 17
232 549 568 586 605 624 642 661 680 698 717 2 4 6 7 9 11 13 15 17
233 736 754 773 791 810 829 847 866 884 903 2 4 6 7 9 11 13 15 17
234 922 940 959 977 996 014 033 051 070 088 2 4 6 7 9 11 13 15 17
235 37 107 125 144 162 181 200 218 236 254 273 2 4 6 7 9 II 13 15 17
236 291 310 328 346 365 383 401 420 438 457 2 4 6 7 9 11 13 15 17
237 475 493 511 530 548 566 585 603 621 639 2 4 5 7 9 11 13 15 16
238 658 676 694 712 731 749 767 785 803 822 2 4 5 7 9 11 13 15 16
239 840 858 876 894 912 931 949 967 985 003 2 4 5 7 9 11 13 14 16
240 38 021 039 057 075 093 112 130 148 166 184 2 4 5 7 9 11 13 14 16
241 202 220 238 256 274 292 310 328 346 364 2 4 5 7 9 II 13 14 16
242 382 399 417 435 453 471 489 507 525 543 2 4 5 7 9 II 13 14 16
243 561 578 596 614 632 650 668 686 703 721 2 4 5 7 9 II 12 14 16
244 739 757 775 792 810 828 846 863 881 899 2 4 5 7 9 11 12 14 16
245 917 934 952 970 987 005 023 041 058 076 2 4 5 7 9 11 12 14 16
246 39 094 III 129 146 164 182 199 217 235 252 2 4 5 7 9 11 12 14 16
247 270 287 305 322 340 358 375 393 410 428 2 4 5 7 9 11 12 14 16
248 445 463 480 498 515 .533 550 568 585 602 2 3 5 7 9 10 12 14 16
249 620 637 655 672 690 7071724 742 759 777 2 3 5 7 9 10 12 14 16
250 794 811 829 846 863 881 898 915 933 950 2 3 5 7 9 10 12 14 16
0 1 2 3 4 I 5 I 6 7 8 9 I1 2 3 4 I 5 I 6 7 8 9
30 103-'39 950
890 FIVE-FIGURE LOGARITHMS: 250~300
250
I 0
39 794
1
811
2 3
829 846 863
4 I 5
881
I 6 7 8
898 915 933 950
9
11 2 p:Or:R1TI:Nt:A;TS8
2 3 5 7 9 10 12 14
9
16
0'
\ >
251 967 985 002 019 037 054 071 088 106 123 2 3 5 7 9 10 12 14 16
252 40 140 157 174 192 209 226 243 261 278 295 2 3 5 7 9 10 12 14 15
253 312 329 346 364 381 398 415 432 449 466 2 :I 5 7 9 10 12 14 15
254 483 500 518 535 552 569 586 603 620 637 2 3 5 7 9 10 12 14 15
255 654 671 688 705 722 739 756 773 790 807 2 3 5 7 8 10 12 14 15
256 824 841 858 875 892 909 926 943 959 976 2 3 5 7 8 10 12 14 15
257 993 010 027 044 061 078 095 111 128 145 2 3 5 7 8 10 12 13 15
258 41 162 179 196 212 229 246 263 280 296 313 2 3 .5 7 8 10 12 13 15
259 330 347 363 380 397 414 430 447 464 481 2 3 .5 7 8 10 12 13 15
260 497 .514 531 547 564 581 597 614 631 647 2 3 5 7 8 10 12 13 15
261 664 680 697 714 731 747 764 781 797 814 2 3 .5 7 8 10 12 13 1.5
262
263
264
830
996
42 160
847 863 880 896
012 029 045 062
177 193 209 226
913
078
243
929 946 963 979
095 111 127 143
259 275 292 308
2 3
2 :I
2 3
5
5
.5
7
7
7
8
8
8
10
10
10
12
12
11
13
13
13
15
1.5
15
--
265 325 341 357 374 390 406 423 439 455 472 2 3 5 7 8 10 11 13 15
266 488 504 521 537 553 570 586 602 619 635 2 3 5 7 8 1011 13 15
267 651 667 684 700 716 732 749 765 781 797 2 3 5 6 8 10 11 13 15
268 813 830 846 862 878 894 910 927 943 959 2 3 5 6 8 1011 13 15
269 975 991 008 024 040 056 072 088 104 120 2 3 5 6 8 10 11 13 14
270 43 136 152 169 185 201 217 233 249 265 281 2 3 5 6 8 10 11 13 14
271 297 313 329 345 361 377 393 409 42.5 441 2 3 5 6 8 10 11 13 14
272 4.57 473 489 505 521 537 553 569 .585 600 2 3 5 6 8 10 11 13 14
273 616 632 648 664 680 696 712 727 743 759 2 3 5 6 8 10 11 13 14
274 775 791 807 823 838 854 870 886 902 917 2 3 5 6 8 10 11 13 14
275 933 949 965 981 996 012 028 044 059 075 2 :I 5 6 8 911 13 14
276 44 091 017 122 138 154 170 185 201 217 232 2 3 5 6 8 9 11 13 14
277 248 264 279 295 311 326 342 358 373 389 2 3 5 6 8 911 13 14
278 404 420 436 451 467 483 498 514 529 545 2 :I 5 6 8 9 11 12 14
279 560 576 592 607 623 638 654 669 685 700 2 3 5 6 8 9 11 12 14
280 716 731 747 762 778 793 809 824 840 855 2 3 5 6 8 9 11 12 14
281 871 886 902 917 932 948 963 979 994 010 2 3 5 6 8 9 11 12 14
282 45 025 040 056 071 086 102 117 133 148 163 2 3 5 6 8 911 12 14
283 179 194 209 225 240 255 271 286 301 317 2 3 5 6 8 9 11 12 14
284 332 347 362 378 393 408 423 439 4.54 469 2 3 5 6 8 9 11 12 14
285 484 500 515 530 545 560 576 591 606 621 2 3 5 6 8 9 11 12 14
286 637 652 667 682 697 712 728 743 758 773 2 3 5 6 8 9 11 12 14
287 788 803 818 834 849 864 879 894 909 924 2 3 5 6 8 911 12 14
288 939 954 969 984 000 015 030 045 060 075 2 3 5 6 8 9 11 12 14
289 46 090 105 120 135 150 165 180 195 210 225 1 3 4 6 8 9 10 12 13
290 240 255 270 285 300 315 330 344 359 374 1 3 4 6 7 9 10 12 13
291 389 404 419 434 449 464 479 494 509 523 1 3 4 6 7 9 10 12 13
292 538 553 568 583 598 613 627 642 6.57 672 1 3 4 6 7 9 10 12 13
293 687 702 716 731 746 761 776 790 805 820 1 3 4 6 7 9 10 12' 13
294 835 849 864 879 894 909 923 938 953 967 1 3 4 6 7 9 10 12 13
295 982 997 012 026 041 056 070 085 100 114 1 3 4 6 7 910]213
296 47 129 144 159 173 188 202 217 232 246 261 1 3 4 6 7 9 10 12 13
297 276 290 305 319 334 349 363 378 392 407 1 3 4 6 7 9 10 12 13
298 422 436 451 466 480 494 509 524 538 553 1 3 4 6 7 9 10 12 13
299 567 582 596 611 625 640 654 669 683 698 1 3 4 6 7 9 10 12 13
300 712 727 741 756 770 784 799 813 828 842 1 3 4 6 7 9 10 12 13
I 0 1 2 3 4 I 5 I 6 7 8 9 I1 2 3 41 5 1 6 7 8 9
'39 794-'47 842
FIVE-FIGURE LOGARITHMS: 300-350 891
0 1 2 3 4 I 5 II 6 7 8 9 1 2 3 41 5 I 6 7 8 9
300 47 712 727 741 756 770 784 799 813 828 842 1 3 4 6 7 9 10 12 13
301 857 871 885 900 914 929 943 959 972 986 I 3 4 6 7 9 10 12 13
302 48 001 015 029 044 058 073 087 101 116 130 I 3 4 6 7 9 10 11 13
303 144 159 173 187 202 216 230 244 258 273 I 3 4 6 7 9 10 11 13
304 287 302 316 330 344 359 373 387 401 416 I 3 4 6 7 9 10 11 13
305 430 444 458 473 487 501 515 530 544 558 1 3 4 6 7 9 10 11 13
306 572 586 601 615 629 643 657 671 686 700 I 3 4 6 7 9 10 11 13
307 714 728 742 756 770 785 799 813 827 841 I 3 4 6 7 8 10 11 13
308 855 869 883 887 911 926 940 954 968 982 1 3 4 6 7 8 10 11 13
309 996 010 024 038 058 066 080 094 108 122 I 3 4 6 7 8 10 11 13
310 49 136 150 164 178 192 206 220 234 248 262 I3 4 6 7 8 10 11 13
311 276 290 304 318 332 346 360 374 388 402 I3 4 6 7 8 10 11 13
312 415 429 443 457 471 485 499 513 527 541 1 3 4 6 7 8 10 11 13
313 554 568 582 596 610 624 638 651 665 679 I 3 4 6 7 8 10 11 12
314 693 707 721 734 748 762 776 790 803 817 1 3 4 6 7 8 10 11 12
315 831 845 859 872 886 900 914 927 941 955 I 3 4 5 7 8 10 11 12
316 969 983 996 010 024 087 051 065 079 092 1 3 4 5 7 8 10 11 12
317 50 106 119 133 147 161 174 188 202 215 229 I 3 4 5 7 8 10 11 12
318 243 256 270 284 297 311 325 338 352 365 I 3 4 5 7 8 10 11 12
319 379 393 407 420 433 447 461 474 488 501 I 3 4 5 7 8 10 11 12
320 515 529 542 556 569 583 596 610 624 637 I 3 4 5 7 8 9 11 12
321 650 664 678 691 705 718 732 745 759 772 I 3 4 5 7 8 9 11 12
322 786 799 813 826 839 853 866 880 893 907 I 3 4 5 7 8 9 11 12
323 920 934 947 961 974 987 001 014 028 041 1 3 4 5 7 8 9 11 12
324 51 054 068 081 095 108 121 135 148 161 175 1 3 4 5 7 8 9 11 12
325 188 202 215 228 242 255 268 282 295 308 I 3 4 5 7 8 9 11 12
326 322 335 348 362 375 388 402 415 428 442 I 3 4 5 7 8 9 11 12
327 455 468 481 495 508 521 534 548 561 574 I 3 4 5 7 8 9 11 12
328 587 601 614 627 640 654 667 680 693 706 1 3 4 5 7 8 911 12
329 720 733 746 759 772 786 799 812 825 838 1 3 4 5 7 8 9 11 12
330 851 865 878 891 904 917 930 943 957 970 I 3 4 5 7 8 9 11 12
331 983 996 009 022 035 048 061 075 088 101 I 3 4 5 7 8 9 10 12
332 52 114 127 140 153 166 179 192 205 218 231 1 3 4 5 7 8 9 10 12
333 244 257 270 284 297 310 323 336 349 362 1 3 4 5 7 8 9 10 12
334 375 388 401 414 427 440 453 466 479 492 1 3 4 5 6 8 9 10 12
335 504 517 530 543 556 569 582 595 608 621 I 3 4 5 6 8 9 10 12
336 634 647 660 673 686 699 711 724 737 750 1 3 4 5 6 8 9 10 12
337 763 776 789 802 815 827 840 853 866 879 I 3 4 5 6 8 9 10 12
338 892 905 917 930 943 956 969 982 994 007 1 3 4 5 6 8 9 10 12
339 53 020 033 046 058 071 084 097 110 122 135 I 3 4 5 6 8 9 10 12
340 148 161 173 186 199 212 224 237 250 263 I 3 4 5 6 8 9 10 11
341 275 288 301 314 326 339 3.52 364 377 390 I 3 4 5 6 8 9 10 11
342 403 415 428 441 453 466 479 491 504 517 I 3 4 5 6 8 9 10 11
343 529 542 555 567 580 593 605 618 631 643 I 3 4 .~ 6 ! 8 9 10 11
344 656 668 681 694 706 719 732 744 757 769 1 3 4 5 6 8 9 10 11
345 782 794 807 820 832 845 857 870 882 895 1 3 4 5 6 8 9 10 11
346 908 920 933 945 958 970 983 995 008 020 I 3 4 5 6 8 9 10 11
347 54 033 045 058 070 083 095 108 120 133 145 I 2 4 5 6 8 9 10 11
348 158 170 183 195 208 220 233 245 258 270 1 2 4 5 6 7 9 10 11
349 283 295 308 320 332 345 357 369 382 394 I 2 4 5 6 7 9 10 11
350 407 419 432 444 456 469 I 481 494 506 518 1 2 4 5 6 I
7 9 10 11
I 0 1 2 3
I
4 1 5 I 6 7 8 9 11 2 3 41 5 1 6 7 8 9
47 712--'54 518
892 FIVE-FIGURE LOGARITHMS: 350-400
, 0 1 2 3 4 I 5 II 6 7 8 9
PROPORTIONAL PARTS
1 2 3 41 5 1 6 7 8 ~-I
-f
350 54 407 419 432 444 456 469 481 494 506 518 1 2 4 5 6 7 9 10 11
351 531 543 555 568 580 593 605 617 630 642 1 2 4 5 6 7 9 10 n
352 654 667 679 691 704 716 728 741 753 765 1 2 4 5 6 7 9 10 11
353 777 790 802 814 827 839 851 864 876 888 1 2 4 5 6 7 9 10 11
354 900 913 925 937 949 962 974 986 998 011 1 2 4 5 6 7 9 10 11
355 55 023 035 047 060 072 084 096 108 121 133 1 2 4 5 6 7 9 10 11
356 145 157 169 182 194 206 218 230 242 255 1 2 4 5 6 7 9 10 11
357 267 279 291 303 315 328 340 352 364 376 1 2 4 5 6 7 9 10 11
358 388 400 413 425 437 449 461 473 485 497 1 2 4 5 6 7 8 10 11
359 509 522 534 546 558 570 582 594 606 618 1 2 4 5 6 7 8 10 11
360 630 642 654 666 678 691 703 715 727 739 1 2 4 5 6 7 8 10 11
361 751 763 775 787 799 811 823 835 847 859 1 2 4 5 6 7 8 10 11
362 871 883 895 907 919 931 943 955 967 979 1 2 4 5 6 7 8 10 11
363 991 003 015 027 038 050 062 074 086 098 1 2 4 5 6 7 8 10 11
364 56 110 122 134 146 158 170 182 194 205 217 1 2 4 5 6 7 8 10 11
365 229 241 253 265 277 289 301 312 324 336 1 2 4 5 6 7 8 10 11
366 348 360 372 384 396 407 419 431 443 455 1 2 4 5 6 7 8 9 10
367 467 478 490 502 514 526 538 549 561 573 1 2 4 5 6 7 8 910
368 585 597 608 620 632 644 656 667 679 691 1 2 4 5 6 7 8 9 10
369 703 714 726 738 750 761 773 785 797 808 1 2 4 5 6 7 8 9 10
370 820 832 844 855 867 879 891 902 914 926 1 2 4 5 6 7 8 9 10
371 937 949 961 972 984 996 008 019 031 043 1 2 4 5 6 7 8 9 10
372 57 054 066 078 089 101 113 124 136 148 159 1 2 3 5 6 7 8 9 10
373 171 183 194 206 217 229 241 252 264 276 1 2 3 5 6 7 8 9 10
374 287 299 310 322 334 345 357 368 380 392 1 2 3 5 6 7 8 9 10
375 403 415 426 438 449 461 473 484 496 507 1 2 3 fi 6 7 8 9 10
376 519 530 542 553 565 576 588 600 611 623 1 2 3 5 6 7 8 9 \10
377 634 646 657 669 680 692 703 715 726 738 1 2 3 5 6 7 8 910
378 749 761 772 784 795 807 818 830 841 852 1 2 3 5 6 7 8 9 10
379 864 875 887 898 910 921 933 944 955 967 1 2 3 5 6 7 8 9 10
380 978 990 001 013 024 035 047 058 070 081 1 2 3 5 6 7 8 9 10
381 58 092 104 115 127 138 149 161 172 184 195 I 2 3 5 6 7 8 910
382 206 218 229 240 252 263 274 286 297 309 I 2 3 5 6 7 8 9 10
383 320 331 343 354 365 377 388 399 410 422 1 2 3 5 6 7 8 9 10
384 433 444 456 467 478 490 501 512 524 535 1 2 3 5 6 7 8 9 10
385 545 557 569 580 591 602 614 625 636 647 1 2 3 4 6 7 8 9 10
386 659 670 681 692 704 715 726 737 749 760 1 2 3 4 6 7 8 9 10,
387 771 782 794 805 816 827 838 850 861 872 1 2 3 4 6 7 8 9 10
388 883 894 906 917 928 939 9.50 961 973 984 1 2 3 4 6 7 8 9 10
389 995 006 017 028 040 051 062 073 084 095 1 2 3 4 6 7 8 9 10
390 59 106 118 129 140 151 162 173 184 195 207 1 2 3 4 6 7 8 9 10
391 218 229 240 251 262 273 284 259 306 318 1 2 3 4 6 7 8 9 10 .
392 329 340 351 362 373 384 39.5 406 417 428 1 2 3 4 6 7 8 9 10
393 439 450 461 472 483 494 506 517 528 .539 1 2 3 4 6 ~ 7 8 9 10
394 550 .561 572 .583 .594 605 616 627 638 649 1 2 3 4 5 7 8 9 10
395 660 671 682 693 704 715 726 737 748 759 1 2 3 4 5 7 8 9 10
396 770 780 791 802 813 824 835 846 857 868 1 2 3 4 5 7 8 9 10
397 879 890 901 912 923 934 945 956 966 977 1 2 3 4 5 7 8 9 10
398 988 999 010 021 032 043 054 065 076 086 1 2 3 4 5 7 8 9 10
399 60 097 108 119 130 141 152 163 173 184 195 1 2 3 4 5 7 8 9 10
400 206 217 228 239 249 I 260 271 282 293 304 1 2 3 4 5 7 8 9 10
I 0 1 2 3 4 I 5 I 6 7 8 9 11 2 3 41 5 I 6 7 8 9
'54 407-'60 304
FIVE-FIGURE LOGARITHMS : 400-450 893
I
I
I PROPORTIONAL PARTS
o 1 2 341 5 I 6 7 8 9 12341516789
~
400 60 206 217 228 239 249 260 271 282 293 304 1 2 3 4 5 I 7 8 9 10
~
401 314 325 336 347 358 369 379 390 401 412 1 2 3 4 5 6 8 9 10
I 402 423 433 444 455 466 477 487 498 509 520 1 2 3 4 5 6 8 9 10
403 530 541 552 563 574 584 595 606 617 627 1 2 3 4 5 6 8 9 10
404 638 649 660 670 681 692 703 713 724 735 1 2 3 4 5 6 8 9 10
405 745 756 767 778 788 799 810 820 831 842 1 2 3 4 5 6 7 9 10
406 853 863 874 885 895 906 917 927 938 949 1 2 3 4 5 6 7 9 10
407 959 970 981 991 002 013 023 034 045 055 1 2 3 4 5 6 7 9 10
408 61 066 077 087 098 109 119 130 140 151 162 1 2 3 4 5 6 7 9 10
409 172 183 194 204 215 225 236 247 257 268 1 2 3 4 5 6 7 8 10
410 278 289 299 310 321 331 342 352 363 374 1 2 3 4 5 6 7 8 10
411 384 395 405 416 426 437 448 458 469 479 1 2 3 4 5 6 7 8 10
412 490 500 511 521 532 542 553 563 574 584 1 2 3 4 5 6 7 8 9
413 595 606 616 627 637 648 658 669 679 690 1 2 3 4 5 6 7 8 9
414 700 711 721 732 742 752 763 773 784 794 1 2 3 4 5 6 7 8 9
415 805 815 826 836 847 857 868 878 888 899 1 2 3 4 5 6 7 8 9
416 909 920 930 941 951 961 972 982 993 003 1 2 3 4 5 6 7 8 9
417 62 014 024 034 045 055 065 076 086 097 107 1 2 3 4 5 6 7 8 9
418 118 128 138 149 159 170 180 190 201 211 1 2 3 4 5 6 7 8 9
419 221 232 242 252 263 273 284 294 304 315 I 2 3 4 5 6 7 8 9
420 325 335 346 356 366 377 387 397 408 418 1 2 3 4 5 6 7 8 9
421 428 439 449 459 469 480 490 500 511 521 1 2 3 4 5 6 7 8 9
422 531 542 552 562 572 583 593 603 613 624 1 2 3 4 5 6 7 8 9
423 634 644 655 665 675 685 696 706 716 726 1 2 3 4 5 6 7 8 9
424 737 747 757 767 778 788 798 808 818 829 1 2 3 4 5 6 7 8 9
425 839 849 859 870 880 890 900 910 921 931 1 2 3 4 5 6 7 8 9
426 941 951 961 972 982 992 002 012 022 033 1 2 3 4 5 6 7 8 9
427 63 043 053 063 073 083 094 104 114 124 134 1 2 3 4 5 6 7 8 9
428 144 155 165 175 185 195 205 215 225 236 1 2 3 4 5 6 7 8 9
429 246 256 266 276 286 296 306 317 327 337 1 2 3 4 5 6 7 8 9
430 347 357 367 377 387 397 407 417 428 438 I 2 3 4 5 6 7 8 9
431 448 458 468 478 488 498 508 518 528 538 1 2 3 4 5 6 7 8 9
432 548 558 568 579 589 599 609 619 629 639 1 2 3 4 5 6 7 8 9
433 649 659 669 679 689 699 709 719 729 739 1 2 3 4 5 6 7 8 9
434 749 759 769 779 789 799 809 819 829 839 1 2 3 4 5 6 7 8 9
435 849 859 869 879 889 899 909 919 929 939 I 2 3 4 5 6 7 8 9
436 949 959 969 979 988 998 008 018 028 038 1 2 3 4 5 6 7 8 9
437 64 048 058 068 078 088 098 108 118 128 137 I 2 3 4 5 6 7 8 9
438 147 157 167 177 187 197 207 217 227 237 1 2 3 4 5 6 7 8 9
439 246 256 266 276 286 296 306 316 326 335 1 2 3 4 5 6 7 8 9
440 345 355 365 375 385 395 404 414 424 434 1 2 3 4 5 6 7 8 9
441 444 454 464 473 483 493 503 513 523 532 1 2 3 4 5 6 7 8 9
442 542 552 562 572 582 591 601 611 621 631 1 2 3 4 5 6 7 8 9
443 640 650 660 670 680 689 699 709 719 729 1 2 3 4 5 6 7 8 9
444 738 748 758 768 777 787 797 807 816 826 1 2 3 4 5 6 7 8 9
445 836 846 856 865 875 88(', 895 904 914 924 1 2 3 4 5 6 7 8 9
446 933 943 953 963 972 982 992 002 011 021 1 2 3 4 5 6 7 8 9
447 65 031 040 050 060 070 079 089 099 108 118 1 2 3 4 5 6 7 8 9
448 128 137 147 157 167 176 186 196 205 215 1 2 3 4 5 6 7 8 9
449 225 234 244 254 263 273 283 292 302 312 1 2 3 4 5 6 7 8 9
450 321 331 341 350 360 369 379 388 398 408 1 2 3 4 5 6 7 8 9
I 0 1 2 3 4 1 5 I 6 7 8 9 11 2 3 4[ 5 1
6 7 8 9
60 206--65 408
894 FIVE-FIGURE LOGARITHMS: 450-500
\
PROPORTIONAL PARTS ""\
-,1
,-I
0 1 2 3 4 I 5 I 6 7 8 9 11 2 3 41 5 1 6 7 8
~ ;J
450 65 321 331 341 350 360 369 379 388 398 408 1 2 3 4 5 6 7 8 ,
451 418 428 437 447 456 466 475 485 495 504 1 2 3 4 5 6 7 8 id
452
453
514
610
523
619
533
629
543
639
552
648
562
657
571
667
581
676
591
686
600
696
1
1
2
2
3
3
4
4
5
5
6
6
7
7
8 !l
8 ., 1
454 706 715 725 734 744 753 763 772 782 792 1 2 3 4 5 6 7 8 !:'
455 801 811 820 830 839 849 858 868 877 887 1 2 3 4 5 6 7 8 b
~I
456 896 906 916 925 935 944 954 963 973 982 1 2 3 4 5 6 7 8
457 992 001 011 020 030 039 049 058 068 077 1 2 3 4 5 6 7 8
458 66 087 096 106 115 124 134 144 153 162 172 1 2 3 4 5 6 7 8 9,
459 181 191 200 210 219 229 238 247 257 266 1 2 3 4 5 6 7 8 9 i
460 276 285 295 305 314 323 332 342 351 361 1 2 3 4 5 6 7 8 8
461 370 380 389 398 408 417 427 436 445 455 1 2 3 4 5 6 7 8 8
462 464 474 483 492 502 511 521 530 539 549 1 2 3 4 5 6 7 8 8
463 558' 567 577 586 596 605 614 624 633 642 1 2 3 4 5 6 7 8 8
464 652 661 671 680 689 699 708 717 727 736 1 2 3 4 5 6 7 7 8
465 745 755 764 773 783 792 801 811 820 829 1 2 3 4 5 6 7 7 8
466 839 848 857 867 876 885 894 904 913 922 1 2 3 4 5 6 7 7 8
467 932 941 950 960 969 978 987 996 006 015 1 2 3 4 5 6 6 7 8
468 67 025 034 043 052 062 071 080 089 099 108 1 2 3 4 5 6 6 7 8
469 117 127 136 145 154 164 173 182 191 200 1 2 3 4 5 6 6 7 8
470 210 219 228 237 247 256 265 274 284 293 1 2 3 4 5 6 6 7 81
471 302 311 321 330 339 348 357 367 376 385 1 2 3 4 5 6 6 7 8
472 394 403 413 422 431 440 449 459 468 477 1 2 3 4 5 6 6 7 8
473 486 495 504 514 523 532 541 550 560 569 1 2 3 4 5 5 6 7 8
474 578 587 596 605 614 624 633 642 651 660 1 2 3 4 5 5 6 7 8
475 669 678 688 697 706 715 724 733 742 752 1 2 3 4 5 5 6 7 8
476 761 770 779 788 797 806 815. 825 834 843 1 2 3 4 5 5 6 7 8
477 852 861 870 879 888 897 906 915 925 934 1 2 3 4 5 5 6 7 8
478 943 952 961 970 979 988 997 006 015 024 1 2 3 4 5 5 6 7 8
479 68 034 043 052 061 070 079 088 097 106 ll5 1 2 3 4 5 5 6 7 8
480 124 133 142 151 160 169 178 187 196 205 1 2 3 4 5 5 6 7
481 215 224 233 242 251 260 269 278 287 296 1 2 3 4 5 5 6 7 88 I
482
483
305
395
314
404
323
413
332
422
341
431
350
440
359
449
368
458
377
467
386
476
1 2
1 2
3
3
4
4
4
4
5
5
6
6
7
7 -~
7 8
.
484 485 494 502 511 520 529 538 547 556 565 1 2 3 4 4 5 6
485 574 583 592 601 610 619 628 637 646 655 1 2 3 4 4 5 6 7 8
486 664 673 681 690 699 708 717 726 735 744 1 2 3 4 4 5 6 7 8
487 753 762 771 780 789 797 806 815 824 833 1 2 3 4 4 5 6 7 8
488 842 851 860 869 878 886 895 904 913 922 1 2 3 4 4 5 6 7 8
489 931 940 949 958 966 975 984 993 002 011 1 2 3 4 4 5 6 7 8
490 69 020 028 037 046 055 064 073 082 090 099 1 2 3 4 4 5 6 7 8
491 108 117 126 135 144 152 161 170 179 188 1 2 3 4 4 5 6 7 8
492 197 205 214 223 232 241 249 258 267 276 1 2 3 4 4 5 6 7 8
493 285 293 302 311 320 329 338 346 355 364 1 2 3 4 4 5 6 7 8
494 373 381 390 399 408 417 425 434 443 452 1 2 3 4 4 5 6 7 8
495 461 469 478 487 496 504 513 522 531 539 1 2 3 3 4 5 6 7 l>
496 548 557 566 574 583 592 601 609 618 627 1 2 3 3 4 5 6 7 8
497 636 644 653 662 671 679 688 697 705 714 1 2 3 3 4 5 6 7 8
498 723 732 740 749 758 767 775 784 793 801 1 2 3 3 4 5 6 7 8
499 810 819 827 836 845 854 862 871 880 888 1 2 3 3 4 5 6 7 8
500 897 906 914 923 932 940 949 958 966 975 1 2 3 3 4 5 6 7 8
I 0 1 2 3 4 I 5 I 6 7 8 9 I1 2 3 41 5 1 6 7 8 9
65 321-'69 975
FIVE-FIGURE LOGARl'J.'!:UYll) ; i.1UV-uuu
, PROPORTIONAL PARTS
t.
~OO
0
69 897
1
906
2 3
914 923 932
4 5
940
I 6 7 8
949 958 966 975
9 11 2 3 41 5 1 6 7 8 9
1 2 3 3 4 5 6 7 8
,501 984 992 001 010 018 027 036 044 053 062 1 2 3 3 4 5 6 7 8
~i 502 70 070 079 088 096 105 114 122 131 140 148 1 2 3 3 4 5 6 7 8
503 157 165 174 183 191 200 209 217 226 234 1 2 3 3 4 5 6 7 8
,504 243 252 260 269 278 286 295 303 312 321 1 2 3 3 4 5 6 7 8
i,, .505 329 338 346 355 364 372 381 389 398 406 1 2 3 3 4 5 6 7 8
l 506 415 424 432 441 449 458 467 475 484 492 1 2 3 3 4 5 6 7 8
507 501 509 518 526 535 544 552 561 569 578 1 2 3 3 4 5 6 7 8
508 586 595 603 612 621 629 638 646 655 663 1 2 3 3 4 5 6 7 8
509 672 680 689 697 706 714 723 731 740 748 1 2 3 3 4 5 6 7 8
510 757 766 774 783 791 800 808 817 825 834 1 2 3 3 4 5 6 7 8
511 842 851 859 868 876 885 893 902 910 919 1 2 3 3 4 5 6 7 8
512 927 935 944 952 961 969 978 986 995 003 1 2 3 3 4 5 6 7 8
513 71 012 020 029 037 046 054 062 071 079 088 1 2 3 3 4 5 6 7 8
514 096 105 113 122 130 139 147 155 164 172 1 2 3 3 4 5 6 7 8
515 181 189 198 206 214 223 231 240 248 257 1 2 3 3 4 5 6 7 8
516 265 273 282 290 299 307 315 324 332 341 1 2 3 3 4 5 6 7 8
517 349 357 366 374 383 391 399 408 416 425 1 2 3 3 4 5 6 7 8
518 433 441 450 458 466 475 483 492 500 508 1 2 3 3 4 5 6 7 8
519 517 525 533 542 550 559 567 575 584 592 1 2 2 3 4 5 6 7 8
520 600 609 617 625 634 642 650 659 667 675 1 2 2 3 4 .5 6 7 8
521 684 692 700 709 717 725 734 742 750 759 1 2 2 3 4 5 6 7 8
522 767 775 784 792 800 809 817 825 834 842 1 2 2 3 4 5 6 7 7
523 850 858 867 875 883 892 900 908 917 925 1 2 2 3 4 5 6 7 7
524 933 941 950 958 966 975 983 991 999 008 1 2 2 3 4 5 6 7 7
525 72 016 024 032 041 049 057 066 074 082 090 1 2 2 3 4 5 6 7 7
526 099 107 115 123 132 140 148 156 165 173 1 2 2 3 4 5 6 7 7
527 181 189 198 206 214 222 230 239 247 255 1 2 2 3 4 5 6 7 7
528 263 272 280 288 296 304 313 321 329 337 1 2 2 3 4 5 6 7 7
529 346 354 362 370 378 387 395 403 411 419 1 2 2 3 4 5 6 7 7
] 530 428 436 444 452 460 469 477 485 493 501 1 2 2 3 4 5 6 7 7
531 509 518 526 534 542 550 558 567 575 583 1 2 2 3 4 5 6 7 7
1:;'l2 591 599 607 616 624 632 640 648 656 66'5 1 2 2 3 4 5 6 7 7
,,3 673 681 689 697 705 713 722 730 738 746 1 2 2 3 4 5 6 7 7
534 754 762 770 779 787 795 803 811 819 827 1 2 2 3 4 5 6 6 7
53~ 835 843 852 860 868 876 884 892 900 908 1 2 2 3 4 5 6 6 7
536 916 925 933 941 949 957 965 973 981 989 1 2 2 3 4 5 6 6 7
537 997 006 014 022 030 038 046 054 062 070 1 2 2 3 4 5 6 6 7
538 73 078 086 094 102 III 119 127 135 143 151 1 2 2 3 4 5 6 6 7
539 159 167 175 183 191 199 207 215 223 231 1 2 2 3 4 5 6 6 7
540 239 247 255 264 272 280 288 296 304 312 1 2 2 3 4 5 6 6 7
541 320 328 336 344 352 360 368 376 384 392 1 2 2 3 4 5 6 6 7
542 400 408 416 424 432 440 448 456 464 472 1 2 2 3 4 5 6 6 7
543 480 488 496 504 512 520 528 536 544 552 1 2 2 3 4 5 6 6 7
544 560 568 576 584 592 600 608 616 624 632 1 2 2 3 4 5 6 6 7
545 640 648 656 664 672 679 687 695 703 711 1 2 2 3 4 5 6 6 7
546 719 727 735 743 751 759 767 775 783 791 1 2 2 3 4 5 6 6 7
547 799 807 815 S23 830 838 846 854 862 870 1 2 2 3 4 5 6 6 7
548 878 886 894 902 910 918 926 933 941 949 1 2 2 3 4 5 6 6 7
549 957 965 973 981 989 997 005 013 020 028 1 2 :2 3 4 5 6 6 7
550 74 036 044 052 060 068 076 084 092 099 107 1 2 2 3 4 5 6 6 7
I 0 1 2 3 4 1 5 I 6 7 8 9 1 2 3 41 5 1 6 7 8 9
,69 897-74 107
896 FIVE-FIGURE LOGARITHMS: 550-600
550
551
I 74 036
115
0 1
044
123
2
052
131
3 4
060
139
068
147
I
076
155
I
5 I 6
084
162
7
092
170
8
099
178
9
107
186
11
1
1
PROPORTIONAL PARTS
2 3 41 5 1 6 7 8 ~
2
2
2
2
3
3
4
4
5 6 6 ~,
5 6 6 7
~,
552 194 202 210 218 225 233 241 249 257 265 1 2 2 3 4 5 6 6 7
553 273 280 288 296 304 312 320 327 335 343 1 2 2 3 4 5 5 6 7
554 351 359 367 374 382 390 398 406 414 421 1 2 2 3 4 5 5 6 7
555 429 437 445 453 461 468 476 484 492 500 I 2 2 3 4 5 5 6 7
556 507 515 523 531 539 547 554 562 570 .578 1 2 2 3 4 ,5 .'5 6 7
557 586 593 601 609 617 624 632 640 648 656 1 2 2 3 4 5 fi 6 7
558 663 671 679 687 695 702 710 718 726 733 1 2 2 3 4 5 5 6 7
559 741 749 757 764 772 780 788 796 803 811 1 2 2 3 4 5 5 6 7
560 819 827 834 842 850 858 865 873 881 889 1 2 2 3 4 5 5 6 7
561 896 904 912 920 927 935 943 950 958 966 1 2 2 3 4 5 5 6 7
562 974 981 989 997 005 012 020 028 035 043 1 2 2 3 4 5 5 6 7
563 75 051 059 066 074 082 089 097 105 113 120 1 2 2 3 4 5 5 6 7
564 128 136 143 151 159 166 174 182 189 197 1 2 2 3 4 5 5 6 7
565 205 213 220 228 236 243 251 259 266 274 1 2 2 3 4 5 5 6 7
566 282 289 297 305 312 320 328 335 343 351 1 2 2 3 4 5 5 6 7
567 358 366 374 381 389 397 404 412 420 427 1 2 2 3 4 5 5 6 7
568 435 442 450 458 465 473 481 488 496 504 1 2 2 3 4 5 5 6 7
569 511 519 526 534 542 549 .557 565 572 580 1 2 2 3 4 5 5 6 7
570 587 595 603 610 618 626 633 641 648 656 1 2 2 3 4 5 5 6 7
571 664 671 679 686 694 702 709 717 724 732 1 2 2 3 4 5 5 6 7
572 740 747 755 762 770 778 785 793 800 808 1 2 2 3 4 5 5 6 7
573 815 823 831 838 846 853 861 868 876 884 1 2 2 3 4 5 5 6 7
574 891 899 906 914 921 929 937 944 952 959 1 2 2 3 4 5 5 6 7
575 967 974 982 989 997 005 012 020 027 035 1 2 2 3 4 5 5 6 7
576 76 042 050 057 065 072 080 087 095 103 110 1 2 2 3 4 5 5 6 7
577 118 125 133 140 148 155 163 170 178 185 1 2 2 3 4 5 5 6 7
578 193 200 208 215 223 230 238 245 253 260 1 2 2 3 4 5 -5 6 7
579 268 275 283 290 298 305 313 320 328 335 1 2 2 3 4 5 5 6 7
580 343 350 358 365 373 380 388 395 403 410 1 2 2 3 4 4 5 6 7
581 418 425 433 440 448 455 462 470 477 485 1 2 2 3 4 4 5 6 7
582 492 500 507 515 522 530 537 544 552 559 1 1 2 3 4 4 5 6 7
583 567 574 582 589 597 604 612 619 626 634 1 1 2 3 4 4 5 6 7
584 641 649 656 664 671 678 686 693 701 708 1 1 2 3 4 4 5 6 7
585 716 723 730 738 745 753 760 768 775 782 1 1 2 3 4 4 5 6 7
586 790 797 805 812 819 827 834 842 849 856 1 1 2 3 4 4 5 6 7
587 864 871 879 886 893 901 908 916 923 930 1 1 2 3 4 4 5 6 7
588 938 945 952 960 967 975 982 989 997 004 1 1 2 3 4 4 5 6 7
589 77 0~2 019 026 034 041 048 056 063 070 078 1 1 2 3 4 4 5 6 7
590 085 093 100 107 115 122 129 137 144 151 1 1 2 3 4 4 5 6 7
591 159 166 173 181 188 195 203 210 218 225 1 1 2 3 4 4 5 6 7
592 232 240 247 254 262 269 276 283 291 298 1 1 2 3 4 4 5 6 7
593 305 313 320 327 335 342 349 357 364 371 1 1 2 3 4 4 5 6 7
594 379 386 393 401 408 415 422 430 4il7 444 1 1 2 3 4 4 5 6 7
595 452 459 466 474 481 488 495 503 510 517 1 1 2 3 4 4 5 6 7
596 525 532 539 546 554 561 568 576 583 590 1 1 2 3 4 4 5 6 7
597 597 605 612 619 627 634 641 648 656 663 1 1 2 3 4 4 5 6 7
598 670 677 685 692 699 706 714 721 728 735 1 1 2 3 4 4 5 6 7
599 743 750 757 764 772 779 786 793 801 808 1 1 2 3 4 4 5 6 7
600 815 822 830 837 844 851 859 866 875 880 1 1 2 3 4 4 5 6 7
I 0 1 2 3 4 1 5 1 6 7 8 9 1 2 3 41 5 1
6 7 8 {
"I 0 1 2 3 4 \
5 \ 6 7 8 9
PROPORTIONAL PARTS
1 2 3 41 5 1 6 7 8 9
~~
77 815 822 830 837 844 851 859 866 873 880 1 I 2 3 4 4 5 6 7
887 895 902 909 916 924 931 938 945 952 1 1 2 3 4 4 5 6 7
602 960 967 974 981 988 996 003 010 017 024 I I 2 3 4 4 5 6 6
603 78 032 039 046 053 061 068 075 082 089 096 1 1 2 3 4 4 5 6 6
604 104 III 118 125 132 140 147 154 161 168 1 1 2 3 4 4 5 6 6
605 176 183 190 197 204 211 219 226 233 240 1 1 2 3 4 4 5 6 6
606 247 254 262 269 276 283 290 297 305 312 1 1 2 3 4 4 5 6 6
607 319 326 333 340 347 355 362 369 376 383 1 1 2 3 4 4 5 6 6
608 390 398 405 412 419 426 433 440 447 455 1 1 2 3 4 4 5 6 6
609 462 469 476 483 490 497 504 512 519 526 1 1 2 3 4 4 5 6 6
610 533 540 547 554 561 569 576 583 590 597 1 1 2 3 4 4 5 6 6
611 604 611 618 625 633 640 647 654 661 668 1 1 2 3 4 4 5 6 6
612 675 682 689 696 704 7ll 718 725 732 739 1 1 2 3 4 4 5 6 6
613 746 753 760 767 774 781 789 796 803 810 1 1 2 3 4 4 5 6 6
614 817 824 831 838 845 852 859 866 873 880 1 1 2 3 4 4 5 6 6
I 615 888 895 902 909 916 923 930 937 944 951 1 1 2 3 4 4 5 6 6
616 958 965 972 979 986 993 000 007 014 021 1 1 2 03 4 4 5 6 6
) 617 79 029 036 043 050 057 064 071 078 085 092 1 I 2 3 4 4 5 6 6
618 099 106 113 120 127 134 141 148 155 162 1 1 2 3 4 4 5 6 6
619 169 176 183 190 197 204 211 218 225 232 1 1 2 3 4 4 5 6 6
620 239 246 253 260 267 274 281 288 295 302 1 1 2 3 4 4 5 6 6
621 309 316 323 330 337 344 351 358 365 372 1 1 2 3 4 4 5 6 6
622 379 386 393 400 407 414 421 428 435 442 1 1 2 3 4 4 5 6 6
623 449 456 463 470 477 484 491 498 505 512 1 1 2 3 3 4 5 6 6
624 518 525 532 539 546 553 560 567 574 581 1 1 2 3 3 4 5 6 6
625 588 595 602 609 616 623 630 637 644 650 1 1 2 3 3 4 5 6 6
626 '657 664 671 678 685 692 699 706 713 720 1 1 2 3 3 4 5 6 6
627 127 734 741 748 754 761 768 775 782 789 1 1 2 3 3 4 5 6 6
628 796 803 810 817 824 831 837 844 851 858 1 1 2 3 3 4 5 6 6
629 865 872 879 886 893 900 906 913 920 927 1 1 2 3 3 4 5 6 6
630 934 941 948 955 962 969 975 982 989 996 1 1 2 3 3 4 5 6 6
631 80 003 010 017 024 030 037 044 051 058 065 1 1 2 3 3 4 5 6 6
632 072 079 085 092 099 106 1I3 120 127 134 1 1 2 3 3 4 5 5 {)
633 140 147 154 161 168 175 182 188 195 202 1 1 2 3 3 4 5 5 6
634 209 216 223 229 236 243 250 257 264 271 1 1 2 3 3 4 5 5 6
635 277 284 291 298 305 312 318 325 332 339 1 1 2 3 3 4 5 5 ()
636 346 353 359 366 373 380 387 393 400 407 1 1 2 3 3 4 5 5 ()
637 414 421 428 434 441 448 455 462 468 475 1 1 2 3 3 4 5 5 ()
638 482 489 496 502 509 516 523 530 536 543 1 1 2 3 3 4 5 5 II
639 550 557 564 570 577 584 591 598 604 61I 1 1 2 3 3 4 5 5
II
640 618 625 632 638 645 652 659 665 672 679 1 1 2 3 3 4 5 5 ()
641 686 693 699 706 713 720 726 733 740 747 1 1 2 3 3 4 5 5 ()
642 754 760 767 774 781 787 794 801 808 814 1 1 2 3 3 4 5 5
643 821 828 835 841 848 855 862 868 875 882 1 1 2 3 3 4 5 5 II()
644 889 895 902 909 916 922 ;)29 936 942 949 1 1 2 3 3 4 5 5 ()
645 956 963 969 976 983 990 996 003 010 017 1 I 2 3 3 4 5 5
646 81 023 030 037 043 050 057 064 070 077 084 1 1 2 3 3 4 5 5 II
647 090 097 104 III 117 124 131 137 144 151 1 1 2 3 3 4 5 5 6
648 158 164 171 178 184 191 198 204 211 218 1 1 2 3 3 4 5 5 II
649 224 231 238 245 251 258 265 271 278 285 1 1 2 3 3 4 5 5 6
6
650 291 298 305 311 318 325 331 338 345 351 1 1 2 3 3 4 5 5
6
0 1 2 3 4 I 5 6 7 8 9 1 2 3 41 5 1
6 7 8'jj
-77 815--81 351 ............
:.
898 FIVE-FIGURE LOGARITHMS: 650-700
PROPORTlO~AL PARTS ~".
j o 1 2 3 7 8 234151678b-o
650
651
652
81 291
358
425
298
365
431
305
371
438
311
378
445
318
385
451
325
391
458
331
398
465
338
405
471
345
411
478
351
418
485
~ ~ ~ ~ ~
112334556
I! ~ ~ "f
653 491 498 505 511 518 525 531 538 544 551 1 123 3 455 6
654 558 564 571 578 584 591 598 604 611 618 112334556
655 624 631 637 644 651 657 664 671 677 684 1 1 2 3 3 4 5 5 6
656 690 697 704 710 717 723 730 737 743 750 1 1 2 3 3 4 5 5 6
657 757 763 770 776 783 790 796 803 809"816 1 1 2 3 3 4 5 5 f I
658 823 829 836 842 849 856 862 869 875 882 1 1 2 3 3 4 5 5 '6
659 889 895 902 908 915 921 928 935 941 948 1 1 2 3 3 4 5 5 6
660 954 961 968 974 981 987 994 000 007 014 1 1 2 3 3 4 [, 5 6
661 82 020 027 033 040 046 053 060 066 073 079 1 1 2 3 3 4 5 5 6
662 086 092 099 105 112 119 125 132 138 145 1 1 2 3 3 4 5 5 ,.6
663 151 158 164 171 17~ 184 191 197 204 210 1 1 2 3 3 4 I) 5 ,
664 217 223 230 236 243 250 256 263 269 276 1 1 2 3 3 4 5 5 ;
665 282 289 295 302 308 315 321 328 334 341 I 1 2 3
666 347 354 360 367 374 380 387 393 400 406 I 1 2 3
667 413 419 426 432 439 445 452 458 465 471 1 123
668 478 484 491 497 504 510 517 523 530 536 1 1 2 3
669 543 549 556 562 569 575 582 588 595 601 1 1 2 3
670 607 614 620 627 633 640 646 653 659 666 1 1 2 3
671 672 679 685 692 698 705 711 718 724 730 1 1 2 3
672 737 743 750 756 763 769 776 782 789 795 1 1 2 3
673 802 808 814 821 827 834 840 847 853 860 1 1 2 3
674 866 872 879 885 892 898 905 911 918 924 1 I 2 3
675 930 937 943 950 956 963 969 975 982 988 1 1 2 3 3 4 4 5 6
676 995 001 008 014 020 027 033 040 046 052 1 1 2 3 3 4 4 5 (\
8'i'i S3 959 065 972 07S 085 091 097 104 110 117 1 1 2 3 3 4 4 5 If
678 123 129 136 142 149 155 161 168 174 181 1123"3
679 187 193 200 206 213 219 225 232 238 244 1 1 2 3 3 4 4 5 6 ~
680
681
682
683
684
251
315
378
442
506
257
321
385
448
512
264
327
391
455
518
270
334
398
461
525
276
340
404
468
531
283
347
410
474
537
289
353
417
480
544
296
359
423
487
550
302
366
429
493
556
308
372
436
499
563
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
iii
4
4
4
4
5
5
1111
6
6
685 569 575 582 588 594 601 607 613 620 626 1 1 2 3 3 4 4 5 6"
686 632 639 645 651 658 664 670 677 683 689 1 1 2 3 3 3 4 5 6
687 696 702 708 715 721 727 734 740 746 753 1 1 2 3 3 4 4 5 6
688 759 765 771 778 784 790 797 803 809 816 1 1 2 3 3 4 4 5 6
689 822 828 835 841 847 853 860 866 872 879 1 1 2 3 3 4 4 5 6
690 885 891 898 904 910 916 923 929 935 942 1 1 2 3 :) 4 4 5 6
691 948 954 960 967 973 979 986 992 998 004 1 1 2 3 :) 4 4 5 6
692 84 011 017 023 029 036 042 048 055 061 067 1 1 2 3 3 4 4 5 6
693 073 080 086 092 098 105 111 117 123 130 1 1 2 2 3 4 4 5 6
694 136 142 148 155 161 167 173 180 186 192 1 1 2 2 3 4 4 5 6
695 198 205 211 217 223 230 236 242 248 255 1 1 2 2 3 4 4 .5 6
696 261 267 273 280 286 292 298 305 311 317 1 1 2 2 3 4 4 5 6
697 323 330 336 342 348 354 361 367 373 379 1 1 2 2 3 4 4 5 6
698 386 392 398 404 410 417 423 429 435 442 1 1 2 2 3 4 4 5 6
699 448 454 460 466 473 479 485 491 497 504 1 1 2 2 3 4 4 5 6
700 510 516 522 528 535 541 547 553 559 566 1 1 2 2 3 4 4 5 6
---'~--------------~~----------~------~-+-------I
o 1 2 3 4) 5) 6 7 8 9 1 2 3 4 ) Ii 6 7 8 9
-81 291-'84 566
t.
FIVE-FIGURE LOGAR!THMS: 700-750 899
~. I 0 1 2 3 4 I 5 I 6 7 8 9 11
PROPORTIONAL PARTS
2 3 41 5 1
6 7 8 9
f''I"701
'JO'' ' ' " ,,0 516 522 528 53,;
572 578 584 590 597
541
603
547
609
553
615
659
621
566
628
1
I
1 2 2
I 2 2
3
3
4 4 5 6
4 4 5 6
702 634 640 646 652 658 665 671 677 683 689 1 1 2 2 3 4 4 5 6
703 696 702 708 714 720 726 733 739 745 751 I 1 2 2 3 4 4 5 6
704 757 763 770 776 782 788 794 800 807 813 1 1 2 2 3 4 4 5 6
705 819 825 831 837 844 850 8;')6 862 868 874 1 1 2 2 3 4 4 ;') 6
706 880 887 893 899 905 I 911 917 924 930 936 1 1 2 2 3 4
4
4 5 6
707 942 948 954 960 967 973 979 985 991 997 1 1 2 2 3 4 5 6
708 85 003 009 016 022 028 034 040 046 052 058 1 1 2 2 3 4 4 5 6
709 065 071 077 083 089 095 101 107 114 120 1 1 2 2 3 4 4 5 6
710 126 132 138 144 150 1;)6 163 169 175 181 1 1 2 2 3 4 4 5 6
711 187 193 199 205 211 217 224 230 236 242 1 1 2 2 3 4 4 5 5
712 248 254 260 266 272 278 285 291 297 303 1 1 2 2 3 4 4 5 5
'" .3 309 315 321 327 333 339 345 352 358 364 1 1 2 2 3 4 4 5 5
.4 370 376 382 388 394 400 406 412 418 425 1 1 2 2 3 4 4 5 5
15 431 437 443 449 455 461 467 473 479 485 1 1 2 2 3 14 4 5 5
I "'16 491 497 503 510 516 522
576 582
528
588
534
594
540
600
546
606
1 1
1 1
2 2
2 2
3 4 4 5 5
3 4 4 5 5
; 17 552 558 564 570
718 612 618 625 631 637 '643 649 655 661 667 1 1 2 2 3 4 4 ti 5
719 673 679 685 691 697 703 709 715 721 727 1 1 2 2 3 4 4 5 5
720 733 739 745 751 757 763 769 775 781 788 1 1 2 2 3 4 4 5 5
2 4
~! 721
722
794
854
800
860
806
866
812
872
818
878
824
884
830
890
836
896
842
902
848
908
1 1
1 1 2
2
2
3
3 4
4
4
5 5
5 5
723 914 920 926 932 938 944 950 956 962 968 1 1 2 2 3 4 4 5 5
, 724 974 980 986 992 998 004 010 016 022 028 1 1 2 2 3 4 4 5 5
I
I 725 86 034 040 046 052 058 064 070 076 082 088 1 1 2 2 3 4 4 15 5
I
726
'.27
728
729
094
153
213
273
100
159
219
279
106
165
225
285
112
171
231
291
118
177
237
297
124
183
243
303
130
189
249
308
136
195
255
314
141
201
261
320
147
207
267
326
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
3
3
3
3
4 4
4 4
4 4
4 4
5
5
5
5
5
5
5
5
1730 332 338 344 350 356 362 368 374 380 386 1 1 2 2 3 4 4 5 5
~ 731 392 398 404 410 416 421 427 433 439 445 1 1 2 2 3 4 4 5 5
732 451 457 463 469 475 481 487 493 499 504 1 1 2 2 3 4 4 5 5
733 510 516 522 528 534 540 546 552 558 564 1 1 2 2 3 4 4 5 5
734 570 576 581 587 593 599 605 611 617 623 1 1 2 2 3 4 4 5 5
1
735 629 635 641 646 652 658 664 670 676 682 1 1 2 2 3 4 4 5 5
, 736 688 694 700 705 711 717 723 729 735 741 1 1 2 2 3 4 4 5 5
! 737
738
747
806
753
812
759
817
764
823
770
829
776
835
782
841
788
847
794
553
800
859
1
1
1
1 2
2 2
2
3
3
4
4
4
4
5 5
5 5
739 864 870 876 882 888 894 900 906 9il 917 1 1 2 2 3 4 4 5 5
740 923 929 935 941 947 953 958 964 970 976 1 1 2 2 3 4 4 5 5
741 982 988 994 999 005 011 017 023 029 035 1 1 2 2 3 4 4 5 5
742 87 040 046 052 058 064 070 075 081 087 093 1 1 2 2 3 4 4 5 5
743 099 105 III 116 122 128 134 140 146 151 1 1 2 2 3 4 4 5 5
744 157 163 169 175 181 186 192 198 204 210 1 1 2 2 3 4 4 5 5
745 216 221 227 233 239 245 251 256 262 268 1 1 2 2 3 3 4 5 5
746 274 280 286 291 297 303 309 315 320 326 1 .1 2 2 3 3 4 5 5
747 332 338 344 350 355 361 367 373 379 384 1 1 2 2 3 3 4 5 5
748 390 396 402 408 413 419 425 431 437 442 1 1 2 2 3 3 4 5 5
749 448 454 460 466 471 477 483 489 495 500 1 1 2 2 3 3 4 5 5
750 506 512 518 523 529 535 541 547 552 558 1 1 2 2 3 3 4 5 5
I 0 1 2 3 4 I 5 I 6 7 8 9 I1 2 3 4/ 5 1
6 7 8 9
, . 84 510-'87 558
900 FIVE-FIGURE LOGARITHMS: 750-800
PROPORTIONAL PARTS'" __
0 1 2 3 4 II 5 I 6 7 8 9 1 2 3 41 5 1 6 7 8 9-
750 87 506 512 518 523 529 535 541 547 552 558 1 1 2 2 3 3 4 5 5 j
.,..
751 564 570 576 581 587 593 599 604 610 616 1 1 2 2 3 3 4 5 5 .
752 622 628 633 639 645 651 656 662 668 674 1 1 2 2 3 3 4 5 5\.
753 680 685 691 697 703 708 714 720 726 731 1 1 2 2 3 3 4 5 5 '
754 737 743 749 754 760 766 772 777 783 789 1 1 2 2 3 3 4 5 5
755 795 800 806 812 818 823 829 835 841 846 1 1 2 2 3 3 4 5 5
756 852 858 864 869 875 881 887 892 898 904 1 1 2 2. 3 3 4 5 5
757 910 915 921 927 933 938 944 950 955 961 1 1 2 2 3 3 4 5 5
758 967 973 978 984 990 996 001 007 018 018 1 1 2 2 3 3 4 5 5
759 88 024 030 036 041 047 053 058 064 070 076 1 1 2 2 3 3 4 5 5
760 082 087 093 098 104 110 116 121 127 133 1 1 2 2 3 3 4 5 5
761 138 144 150 156 161 167 173 178 184 190 1 1 2 2 3 3 4 5 5
762 196 201 207 213 218 224 230 235 241 247 1 I 2 2 3 3 4 5 5
763 252 258 264 270 275 281 287 292 298 304 1 1 2 2 3 3 4 5 5
764 309 315 321 326 332 338 343 349 355 360 1 1 .2 2 3 3 4 5 5
765 366 372 378 383 389 395 400 406 412 417 1 1 2 2 3 3 4 5 5
766 423 429 434 440 446 451 457 463 468 474 1 1 2 2 3 3 4 5 5
767 480 485 491 497 502 508 514 519 525 530 1 1 2 2 3 3 4 5 5
768 536 542 547 553 559 564 570 576 581 587 1 1 2 2 3 3 4 5 5
769 593 598 604 610 615 621 627 632 638 643 1 1 2 2 3 3 4 5 5
770 649 655 660 666 672 677 683 689 694 700 1 1 2 2 3 3 4 5 5
771 705 711 717 722 728 734 739 745 750 756 1 1 2 2 3 3 4 5 5
772 762 767 773 779 784 790 795 801 807 812 1 1 2 2 3 3 4 4 5
773 818 824 82~ 835 840 846 852 857 863 868 1 1 2 2 3 3 4 4 5
774 874 880 885 891 897 902 908 913 919 925 1 1 2 2 3 3 4 4 5
775 930 936 941 947 953 958 964 969 975 981 1 1 2 2 3 3 4 4 5
776 986 992 997 003 009 014 020 025 031 037 1 1 2 2 3 3 4 4 5
777 89 042 048 053 059 064 070 076 081 087 092 1 1 2 2 3 3 4 4 5
778 098 104 109 115 120 126 131 137 143 148 1 1 2 2 3 3 4 4 5
779 154 159 165 170 176 182 187 193 198 204 1 1 2 2 3 3 4 4 5
780 209 215 221 226 232 237 243 248 254 260 1 1 2 2 3 3 4 4 5
781 265 271 276 282 287 293 298 304 310 315 1 1 2 2 3 3 4 4 5
782 321 326 332 337 343 348 354 360 365 371 1 1 2 2 3 3 4 4 5
783 376 382 387 393 398 404 409 415 421 426 1 1 2 2 3 3 4 4 5
784 432 437 443 448 454 459 465 470 476 481 1 1 2 2 3 3 4 4 5
785 487 493 498 504 509 515 520 526 531 537 1 1 2 2 3 3 4 4 5
786 542 548 553 559 564 570 575 581 586 592 1 1 2 2 3 3 4 4 5
787 597 603 609 614 620 625 631 636 642 647 1 1 2 2 3 3 4 4 5
788 653 658 664 669 675 680 686 691 697 702 1 1 2 2 3 3 4 4 5
789 708 713 719 724 730 735 741 746 752 757 1 1 2 2 3 3 4 4 5
790 763 768 774 779 785 790 796 801 807 812 1 1 2 2 3 3 4 4 5
791 818 823 829 834 840 845 851 856 862 867 1 1 2 2 3 3 4 4 5
792 873 878 883 889 894 900 905 911 916 922 1 I 2 2 3 3 4 4 5
793 927 933 938 944 949 955 960 966 971 977 1 I 2 2 3 3 4 4 5
794 982 988 993 998 004 009 015 020 026 031 1 1 2 2 3 3 4 4 5
795- 90 037 042 048 053 059 064 069 075 080 086 I -1 2 2 3 3 4 4 5
796 091 097 102 108 113 119 124 129 135 140 1 1 2 2 3 3 4 4 5
797 146 151 157 162 168 173 179 184 189 195 1 1 2 2 3 3 4 4 5
798 200 206 211 217 222 227 233 238 244 249 I I 2 2 3 3 4 4 5
799 255 260 266 271 276 282 287 293 298 304 1 1 2 2 3 3 4 4 5
800 309 314 320 325 331 336 342 347 352 358 1 1 2 2 3 3 4 4 5
0 1 2 3 4 I 5 1 6 7 8 9 1 2 3 41 5 1
6 7 8 9
FIVE-FIGURE LOGARITHMS 800-8aO "U1
I
I
PROPORTIONAL PARTS
I
, 1
0 1 2 3 4 1 5 1 6 7 8 9 2 3 41 5 6 7 8 9
1
'::00 90 309 314 320 325 331 I 336 342 1 2 2
I~
347 352 358 I 3 -4 4 5
801 363 369 374 380 385 I 390 396 401 407 412 1 1 2 2 3 4 4 5
802 417 423 428 434 439 ' 444 450 455 461 466 1 1 2 2 3 '3 4 4 5
803 472 477 482 488 493 499 504 509 515 520 1 1 2 2 3 3 4 4 5
804 526 531 536 542 547 553 . 558 563 569 574 1 1 2 2 3 3 4 4 5
805 580 585 590 596 601 607 612 617 623 628 1 1 2 2 3 3 4 4 5
806 634.639 644 650 655 660 666 671 677 682 1 1 2 2 3 3 4 4 5
807 687 693 698 704 709 714 720 725 730 736 1 1 2 2 3 3 4 4 5
808 741 747 752 757 763 768 773 779 784 789 1 1 2 2 3 3 4 4 5
809 795 800 806 811 816 822 827 832 838 843 1 1 2 2 3 3 4 4 5
810 849 854 859 865 870 875 881 886 891 897 1 1 2 2 3 3 4 4 5
811 902 907 913 918 924 929 934 940 945 950 1 1 2 2 3 3 4 4 5
812 956 961 966 972 977 982 988 993 998 004 1 1 2 2 3 3 4 4 5
813 91 009 014 020 025 030 036 041 046 052 057 I 1 2 2 3 3 4 4 5
814 062 068 073 078 084 089 094 100 105 110 1 1 2 2 3 3 4 4 5
815 116 121 126 132 137 142 148 153 158 164 1 1 2 2 3 3 4 4 5
816 169 174 180 185 190 196 201 206 212 217 1 1 2 2 3 3 4 4 5
817 222 228 233 238 243 249 254 259 265 270 I 1 2 2 3 3 4 4 5
818 275 281 286 291 297 302 307 312 318 323 1 1 2 2 3 3 4 4 5
819 328 334 339 344 350 355 360 365 371 376 1 1 2 2 3 3 4 4 5
820 381 387 392 397 403 408 413 418 424 429 1 1 2 2 3 3 4 4 5
821 434 440 445 450 455 461 466 471 477 482 1 I 2 2 3 3 4 4 5
822 487 492 498 503 508 514 519 524 529 535 1 I 2 2 3 3 4 4 5
823 540 545 551 556 561 566 572 577 582 587 1 1 2 2 3 3 4 4 5
824 593 598 603 609 614 619 624 630 635 640 1 1 2 2 3 3 4 4 5
825 645 651 656 661 666 672 677 682 687 693 1 1 2 2 3 3 4 4 5
826 698 703 709 714 719 724 730 735 740 745 1 1 2 2 3 3 4 4 5
827 751 756 761 766 772 777 782 787 793 798 1 1 2 2 3 3 4 4 5
828 803 808 814 819 824 829 834 840 845 850 1 1 2 2 3 3 4 4 5
829 855 861 866 871 876 882 I 887 892 897 903 1 1 2 2 3 3 4 4 5
830 908 913 918 924 929 934 939 944 950 955 1 1 2 2 3 3 4 4 5
831 960 965 971 976 981 986 991 997 002 007 1 1 2 2 3 3 4 4 5
832 92 012 018 023 028 033 038 044 049 054 059 1 I 2 2 3 3 4 4 5
833 065 070 075 080 085 091 I 096 101 106 III 1 I 2 2 3 3 4 4 5
834 117 122 127 132 137 143 148 153 158 163 I I 2 2 3 3 4 4 5
835 169 174 179 184 189 195 200 205 210 215 1 1 2 2 3 3 4 4 5
836 221 226 231 236 241 247 252 257 262 267 I 1 2 2 3 3 4 4 5
837 273 278 283 288 293 298 304 309 314 319 I 1 2 2 3 3 4 4 5
838 324 330 335 340 345 350 355 361 366 371 1 1 2 2 3 3 4 4 5
839 376 381 387 392 397 402 407 412 418 423 1 1 2 2 3 3 4 4 5
840 428 433 438 443 449 454 459 464 469 474 I 1 2 2 3 3 4 4 5
841 480 485 490 495 500 505 5ll 516 521 526 1 1 2 2 3 3 4 4 5
842 531 536 542 547 552 557 562 567 572 578 1 1 2 2 3 3 4 4 5
843 583 588 593 598 603 609 614 619 624 629 1 1 2 2 3 3 4 4 5
844 634 639 645 650 655 660 665 670 675 681 1 1 2 2 3 3 4 4 5
845 686 691 696 701 706 7ll 716 722 727 732 1 1 2 2 3 3 4 4 5
846 737 742 747 752 758 763 768 773 778 783 1 1 2 2 3 3 4 4 5
847 788 793 799 804 809 814 819 824 829 834 1 1 2 2 3 3 4 4 5
848 840 845 850 855 860 865 870 875 881 886 1 1 2 2 3 3 4 4 5
849 891 896 901 906 911 916 921 927 932 937 1 1 2 2 3 3 4 4 5
850 942 947 952 957 962 967 973 978 983 988 1 1 2 21 3 3 4 4 5
I 0 1 2 3 4 I
5 I 6 7 8 9 I1 2 3 41 5 16 7 8 9
90 309-92 988
902 FIVE-FIGURE LOGARITHMS: 850-900
850
0
92 942
1
947
2 3
952 957 962
4
,
I 5 I 6
967
7 8
973 978 983 988
9 I
1 1 2
PROPORTIONAL PARTS
1 2 3 41 5 1 6 7 8 9
2 3 3 4 4 ~,
851 993 998 003 008 013 018 024 029 034 039 1 1 2 2 3 3 4 4 5
852 93 044 049 054 059 064 069 075 080 085 090 1 1 2 2 3 3 4 4 5
853 095 100 105 110 115 120 125 131 136 141 1 1 2 2 3 3 4 4 5
854 146 151 156 161 166 171 176 181 186 192 0 1 2 2 3 3 4 4 5
855 197 202 207 212 217 222 227 232 237 242 0 1 2 2 3 3 4 4 5
856 247 252 258 263 268 273 278 283 288 293 0 1 2 2 3 3 4 4 5
857 298 303 308 313 318 323 328 334 339 344 0 1 2 2 3 3 4 4 5
858 349 354 359 364 369 374 379 384 389 394 0 1 2 2 3 3 4 4 5
859 399 404 409 41~ 420 425 430 435 440 445 0 1 2 2 3 3 4 4 5
860 450 455 460 465 470 475 480 485 490 495 0 1 2 2 3 3 4 4 5
861 500 505 510 515 520 526 531 536 541 546 0 1 2 2 3 3 4 4 5
862 551 556 561 566 571 576 581 586 591 596 0 1 2 2 3 3 4 4 5
863 601 606 611 616 621 626 631 636 641 646 0 1 2 2 3 3 4 4 5
864 651 656 661 666 671 676 682 687 692 697 0 1 2 2 3 3 4 4 5
865 702 707 712 717 722 727 732 737 742 747 0 1 2 2 3 3 4 4 5
866 752 757 762 767 772 777 782 787 792 797 0 1 2 2 2 3 4 4 5
867 802 807 812 817 822 827 832 837 842 847 0 1 2 2 2 3 4 4 4
868 852 857 862 867 872 877 882 887 892 897 0 1 2 2 2 3 4 4 4
869 902 907 912 917 922 927 932 937 942 947 0 1 2 2 2 3 3 4 4
870 952 957 962 967 972 977 982 987 992 997 0 1 I 2 2 3 3 4 4
871 94 002 007 012 017 022 027 032 037 042 047 0 1 I 2 2 3 3 4 4
872 052 057 062 067 072 077 082 086 091 096 0 1 I 2 2 3 3 4 4
873 101 106 III 116 121 126 131 136 141 146 0 1 1 2 2 3 3 4 4
874 151 156 161 166 171 176 181 186 191 196 0 I I 2 2 3 3 4 4
875 201 206 211 216 221 226 231 236 240 245 0 I 1 2 2 3 3 4 4
876 250 255 260 265 270 275 280 285 290 295 0 I 1 2 2 3 3 4 4
877 300 305 310 315 320 325 330 335 340 344 0 I 1 2 2 3 3 4 4
878 349 354 359 364 369 374 379 384 389 394 0 I 1 2 2 3 3 4 4
879 399 404 409 414 419 424 429 433 438 443 0 1 I 2 2 3 3 4 4
880 448 453 458 463 468 473 478 483 488 493 0 I I 2 2 3 3 4 4
881 498 503 507 512 517 522 527 532 537 542 0 I I 2 2 3 3 4 4
882 547 552 557 562 567 571 576 581 586 591 0 I I 2 2 3 3 4 4
888 596 601 606 611 616 621 626 630 635 640 0 1 1 2 2 3 3 4 4
884 645 650 655 660 665 670 675 680 685 689 0 I I 2 2 3 3 4 4
885 694 699 704 709 714 719 724 729 734 738 0 I I 2 2 3 3 '4 4
886 743 748 753 758 763 768 773 778 783 787 0 I I 2 2 3 3 4 4
887 792 797 802 807 812 817 822 827 832 836 0 1 1 2 2 3 3 4 4
888 84l 846 851 856 861 866 871 876 8S0 885 0 1 1 2 2 3 3 4 4
889 890 895 900 905 910 915 919 924 929 934 0 1 1 2 2 3 4 4 4
890 939 944 949 954 959 963 968 973 978 983 0 1 1 2 2 3 3 4 4
891 988 993 998 002 007 012 017 022 027 032 0 1 1 2 2 3 3 4 4
892 95 036 041 046 051 056 061 066 011 075 080 0 I 1 2 2 3 3 4 4
893 085 090 095 100 105 109 II4 119 124 129 0 I 1 2 2 3 3 4 4
894 134 139 143 148 153 158 163 168 173 177 0 1 1 2 2 3 3 4 4
895 182 187 192 197 202 207 211 216 221 226 0 I I 2 2 3 3 4 4
896 231 236 240 245 250 255 260 265 270 274 0 1 I 2 2 3 3 4 4
897 279 284 289 294 299 303 308 313 318 323 0 I I 2 2 3 3 4 4
898 328 332 337 342 347 352 357 361 366 371 0 1 I 2 2 3 3 4 4
899 376 381 386 390 395 400 405 410 415 419 0 I I 2 2 3 3 4 4
900 424 429 434 439 444 448 453 458 463 468 0 I I 2 2 3 3 4 4
I 0 1 2 3 4 I
I 5 i 6 7 8 9 1 2 3 41 5 I 6 7 8 9
92 942-95 468
FIVE-FIGURE LOGARITHMS: 900-950 903
I. . I
PROPORTIONAL PARTS
i
0 1 2 4 i 5 I 6 7 8 9
3 1 2 3 4 1
I
5 i6 7 8 9
95 424 429 434 439 4441 448 I 453 458 463 468 0 1 1 2 2 3 3 4 4
901 472 477 482 487 492 497 . 501 506 511 516 0 1 1 2 2 3 3 4 4
902 521 525 530 535 540 545 550 554 559 564 0 1 1 2 2 3 3 4 4
903 569 574 578 583 588 593 598 602 607 612 0 1 1 2 2 3 3 4 4
904 617 622 626 631 636 641 646 650 655 660 0 1 1 2 2 3 3 4 4
I
905 665 670 674 679 684 689 694 698 703 708 0 1 1 2 2 3 3 4 4
906 713 718 722 727 732 737 742 746 751 756 0 1 1 2 2 3 3 4 4
907 761 766 770 775 780 785 789 794 799 804 0 1 1 2 2 3 3 4 4
908 809 813 818 823 828 832 837 842 847 852 0 1 I" 2 2 3 3 4 4
909 856 861 866 871 875 880 885 890 895 899 0 1 1 2 2 3 3 4 4
910 904 909 914 918 923 928 933 938 942 947 0 1 1 2 2 3 3 4 4
911 952 957 961 966 971 976 980 985 990 995 0 1 1 2 2 3 3 4 4
912 999 004 009 014 019 023 028 033 038 042 0 1 1 2 2 3 3 4 4
913 96 047 052 057 061 066 071 076 080 085 090 0 1 1 2 2 3 3 4 4
914 095 099 104 109 114 118 123 128 133 137 0 1 1 2 2 3 3 4 4
915 142 147 152 166 161 166 171 175 180 185 0 1 1 2 2 3 3 4 4
916 190 194 199 204 209 213 218 223 227 232 0 1 1 2 2 3 3 4 4
917 237 242 246 251 256 261 265 270 275 280 0 1 1 2 2 3 3 4 4
918 "284289 294298 303 308 313 317 322 327 0 1 1 2 2 3 3 4 4
919 332 336 341 346 350 355 360 365 369 374 0 1 1 2 2 3 3 4 4
920 379 384 388 393 398 402 407 412 417 421 0 1 1 2 2 3 3 4 4
921 426 431 435 440 445 450 454 459 464 468 0 1 1 2 2 3 3 4 4
922 473 478 483 487 492 497 501 506 511 515 0 1 1 2 2 3 3 4 4
923 520 525 530 534 539 544 548 553 558 562 0 1 1 2 2 3 3 4 4
924 567 572 577 581 586 591 595 600 605 609 0 1 1 2 2 3 3 4 4
925 614 619 624 628 633 638 642 647 652 656 0 1 1 2 2 3 3 4 4
926 661 666 670 675 680 685 689 694 699 703 0 1 1 2 2 3 3 ""
4 4
927 708 713 717 722 727 731 736 741 745 750 0 1 1 2 2, 3 3 4 4
928 755 759 764 769 774 778 783 788 792 797 0 1 1 2- 2 3 3 4 4
929 802 806 811 816 820 825 830 834 839 844 0 1 1 2 2 3 3 4 4
930 848 853 858 862 867 872 876 881 886 890 0 1 1 2 2 3 3 4 4
931 895 900 904 909 914 918 923 928 932 937 0 1 1 2 2 3 3 4 4
932 942 946 951 956 960 965 970 974 979 984 0 1 1 2 2 3 3 4 4
933 988 993 997 002 007 011 016 021 025 030 0 1 1 2 2 3 3 4 4
934 97 035 039 044 049 053 058 063 067 072 077 0 1 1 2 2 3 3 4 4
935 081 086 090 095 100 104 109 114 118 123 0 1 1 2 2 3 3 4 4
936 128 132 137 142 146 151 155 160 165 169 0 1 1 2 2 3 3 4 4
937 174 179 183 188 192 197 202 206 211 216 0 1 1 2 2 3 3 4 4
938 220 225 230 234 239 243 248 253 257 262 0 1 1 2 2 3 3 4 4
939 267 271 276 280 285 290 294 299 304 308 0 1 I 2 2 3 3 4 4
940 313 317 322 327 331 336 340 345 350 354 0 1 1 2 2 3 3 4 4
941 359 364 368 373 377 382 387 391 396 400 0 1 1 2 2 3 3 4 4
942 405 410 414 419 424 428 433 437 442 447 0 1 1 2 2 3 3 4 4
943 451 456 460 465 470 474 479 483 488 493 0 1 1 2 2 3 3 4 4
944 497 502 506 511 516 520 525 529 534 539 0 I 1 2 2 3 3 4 4
945 543 548 552 557 562 566 571 575 580 585 0 1 I 2 2 3 3 4 4
946 589 594 598 603 607 612 617 621 626 630 0 I 1 2 2 3 3 4 4
947 635 640 644 649 653 658 663 667 672 676 0 1 1 2 2 3 3 4 4
948 681 685 690 695 699 704 708 713 717 722 0 1 1 2 2 3 3 4 4
949 727 731 736 740 745 750 754 759 763 768 0 1 I 2 2 3 3 4 4
950 772 777 782 786 791 795 800 804 809 813 0 1 1 2
I3 3
4 4 2
I 0 1 2 3 4 1
5 I' 6 7 8 9 I 1 2 3 4! 5 16 7 8 9
95 424-'97 813
904 FIVE-FIGURE LOGARITHMS: 950~1000
I
I I
I
I PROPOItTIONAL PARTS
0 1 2 3 4 I 5 I 6 7 8 9 1 2 3 41 5 :6
I
7 8 9
950 97 772 777 782 786 791 I 795 800 804 809 81:1 0 1 1 2 2 3 3 4 """:-
951 818 823 827 832 8361 841 845 850 855 859 0 1 I 2 2 3 3 4 4
952 864 868 873 877 882 886 891 896 900 905 0 1 1 2 2 3 3 4 4
953 909 914 918 923 928 932 937 941 946 950 0 I I 2 2 3 3 4 4
954 955 959 964 968 973 978 982 987 991 996 0 1 1 2 2 3 3 4 4
955 98 000 005 009 014 019 023 028 032 037 041 0 1 1 2 2 3 3 4 4
956 046 050 055 059 064 068 073 078 082 087 0 1 1 2 2 3 3 4 4
957 091 096 100 105 109 114 118 123 127 132 0 I 1 2 2 3 3 4 4
958 137 141 146 150 155 159 164 168 173 177 0 1 1 2 2 3 3 4 4
959 182 186 191 195 200 204 209 ~14 218 223 0 1 1 2 2 3 3 4 4
,
960 227 232 236 241 245 250 254 259 263 268 0 1 1 2 2 3 3 4 4
961 272 277 281 286 290 295 299 304 308 313 0 1 1 2 2 3 3 4 4
962 318 322 327 331 336 340 345 349 354 358 0 I 1 2 2 3 3 4 4
, 963 363 367 372 376 381 385 390 394 399 403 0 1 I 2 2 3 3 4 4
964 408 412 417 421 426 430 435 439 444 448 0 1 1 2 2 3 3 4 4
965 453 457 462 466 471 475 480 484 489 493 0 1 1 2 2 3 3 4 4
966 498 502 507 511 516 520 525 529 534 538 0 1 1 2 2 3 3 4 4
967 543 547 552 556 561 565 570 574 579 583 0 1 1 2 2 3 3 4 4
968 588 592 597 601 605 610 614 619 623 628 0 1 1 2 2 3 3 4 4
969 632 637 641 646 650 655 659 664 668 673 0 1 1 2 2 3 3 4 4
970 677 682 686 691 695 700 704" 709 713 717 0 1 1 2 2 3 3 4 4
971 722 726 731 735 740 744 749 753 758 762 0 1 1 2 2 3 3 4, 4
972 767 771 776 780 784 789 793 798 802 807 0 1 1 2 2 3 3 4 4
973 811 816 820 825 829 834 838 843 847 851 0 1 1 2 2 3 3 4, 4
974 856 860 865 869 874 878 883 887 892 896 0 1 1 2 2 3 3 4 4
975 900 905 909 914 918 923 927 932 936 941 0 1 1 2 2 3 3 4 4
976 945 949 954 958 963 967 972 976 981 985 0 1 1 2 2 3 3 4 4
977 989 994 998 003 007 012 016 021 025 029 0 1 1 2 2 3 3 4 4
978 99 034 038 043 047 052 056 061 065 069 074 0 1 1 2 2 3 3 4 4
979 078 083 087 092 096 100 105 109 114 118 0 I 1 2' 2 3 3 4, 4
980 123 127 131 136 140 145 149 154 158 162 0 1 1 2 2 3 3 4 4
981 167 171 176 180 185 189 193 198 202 207 0 1 1 2 2 3 3 4 4
982 211 216 220 224 229 233 238 242 247 251 0 1 1 2 2 3 3 4 4
983 255 260 264 269 273 277 282 286 291 295 0 1 1 2 2 3 3 4 4
984 300 304 308 313 317 322 326 330 335 339 0 1 1 2 2 3 3 4 4
985 344 348 352 357 361 366 370 374 379 383 0 1 1 2 2 3 3 4 4
986 388 392 396 401 405 410 414 419 423 427 0 1 1 2 2 3 3 4 4
987 432 436 441 446 449 454 458 463 467 471 0 1 1 2 2 3 3 4 4
988 476 480 484 489 493 498 502 506 511 515 0 1 1 2 2 3 3 4 4
989 520 524 528 533 537 542 546 550 555 559 0 1 1 2 2 3 3 4 4
990 564 568 572 577 581 585 590 594 i599 603 0 1 1 2 2 3 3 4 4,
991 607 612 616 621 625 629 634 638 642 647 0 1 1 2 2 3 3 4 4
992 651 656 660 664 669 673 677 682 686 691 0 1 1 2 2 3 3 4 4
993 695 699 704 708 712 717 721 726 730 734 0 1 1 2 2 3 3 3 4
994 739 743 747 752 756 760 765 769 774 778 0 1 1 2 2 3 3 3 4
995 782 787 791 795 800 804 ' 808 813 817 822 0 1 1 2 2 3 3 3 4
996 826 830 835 839 843 848 I 852 856 861 865 0 1 1 2 2 3 3 3 4
997 870 874 878 883 887 891 896 900 904 909 0 1 1 2 2 3 3 3 4
998 913 917 922 926 930 935 939 944 948 952 0 1 1 2 2 3 3 3 4
999 957 961 965 970 974 978 983 987 991 996 0 1 1 2 2 3 3 3 4
i
I 0 1 2 3 4 i 5 i 6 7 8 9 I1 2 3 41 5 1 6 7 8 9
-97 772-'99 996
INDEX
The following abbreviations are used : -
D. = determination e = electrolytic
v = volumetric gv = gas-volumetric
g = gravimetric p = potentiometric
c = colorimetric m = micro
Absorbents for carbon dioxide, 506: for Ammonia, D. of: in an ammonium salt
water, 506. (v), 246; with Nessler's reagent (c),
Absorbents in gas analysis for: acetylene, 643.
801: benzene, 801: carbon dioxide, Ammonium, D. of: as chloroplatinate (g),
800: carbon monoxide, 803: hydro- 491: by nitrometer (gv), 812.
gen, 803, 804: oxygen, 802: un- Ammoniacal cuprous chloride reagent, 803.
saturated hydrocarbons, 801. Ammoniacal nickel cyanide reagent, 801.
Absorptiometers, 611, 616: commercial Ammonium hexanitro-cerate, 301: puri-
forms of, 616-25: Hilger-Spekker, fication of, 301, 302.
620; use of, 622. Ammonium molybdate reagent, 381, 390.
Absorption apparatus for the determina- Ammonium sulphato-cerate, 301.
tion of carbon dioxide, 5a6, 5a7: Ammonium thiocyanate solution: pre-
coefficient, 599. paration of O'lN, 256: standardisa,
Accelerators, 210. tion of, 257.
Accuracy, definition of, 142. Ampere, 128.
Acetic acid, D. of strength of (v), 240: Amperometric titrations, 36, 769 : cells for,
densities of aqueous solutions of, 851. 772: common types of titration
Acidimetry and alkalimetry, 36, 227: curves, 770, 771: with the dropping
theory of, 47. mercury electrode, technique of, 772,
Acids: common, strengths of, 853: 773; theoretical considerations, 769-
conductometric titrations of, 725-8: 72: D. of lead with standard potas-
densities at 20 C., 851: ionisation sium dichromate solution by, 773: D_
constants of, 7: ionisation of, 1: of nickel with dimethylglyoxime by,
modern views on, 2: polybasic, 1, 8 : 775: D. of sulphate with standard
polybasic, ionisation of, 8: potentio- lead nitrate solution by, 774.
metric titration of, 708: preparation Analysed samples, 855-65: British Chemi-
of standard, 227: strengths of, 5: cal Standards, 857 : British Standard-
strong, 2: weak, 2. ised Steel, 861 : Bureau of Standards,
Activity, 6, 12, 16: coefficient, 6,12,16,17. 861: for students in metallurgical
Activity product, 12. analysis (Ridsdale's), 855: Johnson
Adipic acid, 238. and Matthey Standardised Sub-
Adsorption, 109. stances, 859.
Adsorption current, 739. Analysis: elementary, samples and solu-
Adsorption indicators, 74-6: applications tions for, 854: se-hemes for study of,
of, 251-7: theory of, 74-6. 876, 878.
Agar-potassium chloride bridge, 675, 772. AnhYdrone, 506.
Ageing, of precipitates, 110. Anodes, for electrolytic determinations,
Air baths, 186. 511-14: for polarographic determina-
Alkali, standard, preparation of, 233. tions, 734-7.
Alkaline pyrogallol, 802. Anthranilic acid, 124.
Alkalis, densities of aqueous solutions at Antimony, D. of: as antimonious pyro-
20 C., 853. gallate (g), 436: as tetroxide (g), 435,
Alizarin yellow R, 55. 436: as trisulphide (g), 435, 436: by
Aluminium alloy, analysis of, 581. chloramine-T (v), 376: by iodine (v),
Aluminium, D. of : as oxide (g), 410, 447, 350, 351, 353: by potassium bromate
448: as oxide via basic benzoate (g), (v), 369, 371: by potassium iodate
448, 449: as oxide via basic succinate (v), 362: by potassium iodide-
(g), 448, 449: as oxinate (g), 449: pyridine method (c), 662, 663: by
(m) 836: by aluminon (c), 652, 653 : potassium permanganate (v), 353: in
by oxine (v), 372: in felspar, 589. antimonates (v), 351: in type metal
Aluminon reagent, 652, 653. (v),353.
Amalgamated zinc spirals, 225: prepara- Antimony electrode, 683: applications of,
tion of, 225: use of, 225. 683.
Amaranth, 360, 362. Apparatus: Ambler's portable, 795:
Ambler'S portable apparatus, 795: use of, Bakelite, 180: Bone and Newitt, 799,
'796. 800 : Bone and Wheeler, 798:
905
906 Index
Bunte, 790: fused silica, 179; glass, a-Benzoinoxilb.e (cupron), 121.
178: heating, 185: Hempel, 784: Beryllium, D. of: as oxide (g), 450, 451 ;
iron, 179: micro, for quantitative by ammonium nitrite (g), 451; by
filtration, 823: miscellaneous, for tannin (g), 451, 452: in presence of
micro-analysis: nickel, 179: Orsat- aluminium (g), 452.
Lunge, 792: platinum, 179, 220: Bibliographies, selected: 99, 149, 226,
porcelain, 179: Shepherd, 794 : 396, 596, 672, 717, 733, 768, 777, 813,
silver, 179: U.S. Bureau of Mines, 840.
800. Bimetallic electrode systems, 693.
Arndt's alloy, 248. Bismuth, D. of :' as metal (e), 525: as
Aquametry, 698. oxinate, 426, 427: as oxyiodide (g),
Aqueous vapour, pressure of, 782. 425, 426: as phosphate (g), 426,
Arsenic, D. of: as ammonium uranyl 427: as pyrogallate (g), 425, 426:
arsenate (g), 433, 435: as by cupferron (g), 426, 427: by
MgNH.AsO.,6H 2 0 (g), 435: as mag- potassium iodide (c), 667, 668: in
nesium pyroarsenate (g), 433, 434: lead,668.
as silver arsenate (v), 262: as tri- Blank determination, 146.
sulphide (g), 433, 434: by Gutzeit's Bleaching Powder, D. of available chlorine
method (c), 656, 657-9: by molyb- in : by arsenite method (v), 350: by
denum blue method (c), 656, 661: by iodometric method (v), 349: by
potassium bromate (v), 369, 370: by mtrometer (gv), 812: (p), 711.
potassium iodate (v), 362: by Boiling rods, 180.
Sanger-Black-Gutzeit method (c), Bone and Newitt apparatus, 800.
656, 659-61 : in arsenates, by sodium Bone and Wheeler apparatus, 798.
thiosulphate (v), 351. Borates, D. of: via methyl borate (g),
Arsenious oxide, purification of, 341: 502.
standard solution of, 341, 342. Borax: as standard substance, 231:
Arsenite and arsenate in admixture, D. of determination of (vi, 245: purifica-
(g),434. tion of, 232: titration with strong
Ascarite, 506. acid,67.
Arsonic acids, 123. Borda's method of weighing, 160.
Ashless tablets, 210. Bordeaux indicator, 368, 370.
Atomic weights, table of, 841. Boric acid, D, of: (v), 245.
Available chlorine, 349, 350, 711. Brass, analysis of, 547, 555.
Azolitmin, 55. Brilliant POl).ceau 5R, 360, 362, 368,
370.
Back e.m.f., 130. Bromates, D. of: as silver bromide (g),
Bakelite apparatus, 180. 497: by sodium thiosulphate (v),
Balance: air-damped, 170: arms, in- 347.
equality of, 161, 162: care and use Bromides, D. of: as silver bromide (g),
of, 155: chainomatic, 169: con- 493: by mercurous nitrate (v), 253 :
struction of, 150: description of by merGurous perchlorate (v), 253,
typical analytical, 151: magnetically 254: by silver nitrate (v), 252: by
damped, 170: maximlj.m load of, Volhard's method (v), 259.
153: Mettler gram-atic, 172: micro, Bromo-cresol green, 55.
814 : multiple-rider or multiple- Bromo-cresol purple, 55.
weight, 170: requirements of a good, Bromo-phenol blue, 55: as adsorption
152: semimicro, 174: sensitivity indicatOl:", 253.
curve, 157: sensitivity, determina- Bromo-thymol blue, 55.
tion of, 156: sensitivity of, 156: Bronze, analYsis of, 547, 560.
sensitiyity and maximum load of, Buffer action 31.
153: theory of, 150. Buffer solution, 31-4, 638: tables of,
Balancing method, 604, 608. 868-72.
Barium, D. of: (v), 267: as chromate Buffer standa.rds, 674, 868.
(g), 479, 480: as sulphate (g), 479, "Bumping" of solutions, 180, 187.
480. Bunsen valve, 281.
Barium hydroxide, standard solution of, Bunte burette, 790: use of, 791.
239. Buoyancy of air in weighing, 162.
Barium peroxide, analysis of, with potas- Burette, 35, 197, 200: calibrator, 202:
sium iodate (v), 364. Bunte, 790, Hempel, 784: reader,
Barrier-layer cells, 612. ~OO: Schellbach, 200.
Bases, 2: densities of aqueous solutions Burettes, 35, 197, 200: calibration of,
at 20 C., 853: dissociation constants 201: micro-, 830: standardised,
of, 7: strength of, 5: strong, 2: 203: tolerances of, 203: weight,
weak,2. 203: with glass stopcock, 198: with
Basic acetate method, 117. pinchco()k, 198.
Beaker cover, Fisher" speedy-vap ", 190. Burette holder, 198: Fisher, 199.
Beakers, 178: covers for, 190: micro, Burners: "Amal ", 177: Bunsen, 176:
820. Fisher high-temperature, 177 :
Benedetti-Pichler drier, 819. Meker, 176: micro-, 820: Pitts-
Benzoic acid, 237. burgh universal, 176: Tirril, 17,).
Index . 907
Cadmium, D. of : as CdNH,PO"H 2 0 or as Chromate to chromic salt, 453.
pyrophosphate (g), 428, 430: as Chromic salt to chromate, 453.
anthranilate (g), 428, 430: as metal Chromium, D. of: as barium chromate
(e), 522: as molybdate (g), 427, 428 : (g), 453, 454: as dichromate (c), 652 :
as ,B-naphthaquinoline complex (g), as sesquioxide (g), 452, 453, 454: as
427, 429; (v), 388: as oxinate (g), sesquioxide via mercurous chromate
374: as pyridine thiocyanate (g), 428, (g), 453, 454: by diphenylcarbazide
429: as quinaldinate (g), 428, 430: (c), 651, 652: by ferrous ammonium
by oxine (v), 373. sulphate (p), 712: by potassium
Cadmium reductor, 222: preparation of cyanate (g), 453: by potassium di-
cadmium for, 223: use of, 223. chromate (v), 297: by potassium
Calcium, D. of: as carbonate (g), 411, iodide-potassium iodate (g), 453: in
414: as molybdate (g), 478, 587: as chromite (v), 297: in steel, 570, 573,
oxalate (urea hydrolysis method) (v), 652.
392: as oxalate monohydrate (g), Chromous salts, reductions with, 325.
411; (m), 837: as oxide (g), 411, Chromous sulphate solutions : preparation
414: as tungstate (g), 478: by of O'lN-, 325: standardisation of,
'potassium permanganate (v), 282: in 326: titrations with, 326:
felspar, 590: in limestone or dolo- Cleaning of glass apparatus, 193.
mite, 584, 587. Coagulation values, 107.
Calibration: of burettes, 201: of gas Cobalt, D. of: as anthranilate (g), 461,
burettes, 783: of pipettes, 196: of 462: as metal (e), 461, 524: by a-
volumetric (measuring) flasks, 194: nitroso-,B-naphthol and weighing as
of weights, 164. CoSO" or as Co (g), 461, 462: by
Calomel electrodes, 676-8, 696, 755. nitroso-R-salt (c), 655, 656: by
Carbon dioxide in air, D. of (v), 242. oxine (v), 374: by phenylthio-
Carbon in steel, D. of, 566. hydantoic acid (g), 461, 462: by
Carbon tetrachloride, 331, 360. potassium ferrocyanide solution (p),
Carbonates, D. of: (g), 506; (v), 239. 714: by pyridine-ammonium thio-
Carbonate and bicarbonate, D. in mixtures cyanate method (g), 461, 463; (v),
of (v), 244: and hydroxide, D. in 280: in steel, 576.
mixtures of (v), 242. Colloidal state, 104.
Carbosorb, 506. Colorimeters, 598: Dubosq type, 608:
Casseroles, 179. filter, 598: filters for, 614--16:
Cells: concentration, 80: conductivity, hydrogen ion, 640, 641: photo-
721, 722, 725 ~ oxidation-reduction, electric, 598, 616-25; one-cell type,
81: polarographic, 753, 754: voltaic, 616-20 (" Eel," 616; Hilger Biochem
calculation of the e.m.f. of, 81. absorptiometer, 618; Bausch and
Centrifuge, 182: micro, 823: use of, 823. Lomb" monochromatic," 619; Uni-
Ceric ammonium nitrate, 301 : purification cam G.P. photo-electric, 620); two-
of, 301, 302. cell type, 620-5 (Hilger-Spekker ab-
Ceric ammonium sulphate, 301, 303. sorptiometer, 620; Fisher electro-
Ceric sulphate solutions: advantages of, photometer, 623; Coleman, model 8,
300 : indicators for, 301, 303: 625): plunger type, 608.
oxidising properties of, 300: prepara- Colorimetric analysis, 598: criteria for
tion of O'lN-, 302, 303: standardisa- satisfactory, 641: general discussion
tion of, by arsenious oxide, 303, 304 ; of, 598: some general remarks upon,
by ferrous ammonium sulphate, 304 , 641: visual, 598: theory of, 599.
305, 307; by iron, 305; by potassium Colorimetric titration, 607.
ferrocyanide (anhydrous), 304, 305; Colour change interval, 47.
by sodium oxalate, 307; by sodium Colour measurement, classification of
thiosulphate (anhydrous), 304, 306. methods of, 603.
Cerium, D. of: as ceria via eerie iodate Colour standards, permanent, 603, 606.
(g), 473: by eerie sulphate (v), 310 : Combustion pipette: Ambler, 806 :
by ferrous ammonium sulphate (v), Dennis, 805: Hempel, 787: im-
3Il : by sodium thiosulphate (v), 310. proved, 806.
Character of the deposit, 135. Common ion, quantitative effects of, 14.
Chemical factors, 397: table of, 842. Common ion effect, 9.
Chloramine-T solutions : oxidising proper- Comparator, colour: Hellige, 640: Lovi.
ties of, 376: preparation of O'IN-, bond, 639: method, 639.
376: standardisation of, 376. Completeness of deposition, 132, 529.
Chlorates, D. of: as silver chloride (g), Complex formation reactions, 36: general
496: by sodium thiosulphate (v), 346. discussion of, 250: theory of, 71.
Chlorides, D. of: as silver chloride (g), Complex ions, 18: dissociation or in-
309, 492; (m), 836: by mercurous stability constants of, 19, 20: table
perchlorate (v), 253, 254: by silver of instability constants of, 20.
nitrate (v), 252: by Volhard's Concentration cells, 80.
method (v), 258. Conductance, 718: equivalent, 718: equi-
Chloroform, as indicator, 331, 360. valent, at infinite dilution, 718:
.
Chlorophenol red, 55. ionic, 718, 719: measurement of,
Clubroplatinic acid reagent, 486. 725: specific, 719 .
908 Index
Conductivity bridge, 723: Mullard, 723, Cuprous sulphate-.B-naphthol reagent, 803.
724, 725. Current density, effect upon the character
Conductivity cells. 721-2, 725: platinising of the deposit, 135.
electrodes of, 721 : D. of cell constants Cyanides, D. of: as silver cyanide (g),
of, 722, 723. 494: by silver nitrate (v), 263.
Conductivity water, preparation of, 178. 1 : 2-Cyclohexanedione-dioxime, 444.
Conductometric titrations, 36, 718: ap
paratus and measurements, 720-5: Damping of balances, 170.
applications of, 725-30: general Dead-stop technique. 692, 704, 710.
considerations, 718-20: some experi. Decantation, washing by, 216.
mental details for, 730-2. Decomposition potential, 129.
Congo red, 55. Decomposition voltage, 130: table of, 130.
Control determination, 146. Dehydrite, 506.
Controlled cathode potential electrolysis. Depolariser. 517.
136, 527. Deposit, character of, 135.
Controlled potential at the cathode, applica- Deposition potentials, 134.
tions of : D. of copper in bronze, 545 : Depositions with controlled potential at
D. of copper in copper base and tin the cathode, 527.
base alloys, 545: analysis of bearing Desiccators, 180: desiccants for, 181:
metal, 546: analysis of brass or micro, 816-20; uses of, 181 : vacuum,
bronze, 547. 181-
Controlled potential electro-analysis, 530 : Dessichlora, 506.
apparatus for automatic control of Devarda's alloy, 248.
cathode potential, 530; D.C. output DicWorofiuorescein, 76, 252.
unit for, 532; high tension power Differential titration, 689, 690.
pack for, 537; operation of apparatus, Diffusion current, 738, 739.
539; potentiometer for, 536; valve Digestion, 1l0.
amplifier unit for, 533; valve volt- Di-iododimethylfl.uorescein, 254.
meter for, 534; variac unit for. 532 : Dilution method, 603.
general considerlltions, 136, 527: Dimethylglyoxime, 118, 417, 418: aodiWD
manual apparatus for, 137, 533. salt, llS.
Controlled potential in electrolytic separa- Diphenylamine, 91, 293.
tion of metals, theory of, 136, 528. Diphenylbenzidine, 91, 293.
Copper, D. of: as benzoin oxime (g), 430. Diphenylcarbazide, 76, 264, 651.
432: as cuprous thiocyanate (g), Diphenylthiocarbazone, 644.
430, 431: as metal (e), 519: as Direct weighing, 155.
pyridine thiocyanate (g), 431, 432: Displacement titrations, 66, 728: borax
as quinaldinate (g), 431, 432: as with a strong acid, 67: potassium
salicylaldoximate (g), 430, 432: by cyanide with a strong acid, 66:
dithizone (c), 666, 667: byethylene- sodium carbonate with a strong acid,
diamine (g), 431, 433: by oxine (g), 67.
373: by potassium iodate (v), 362: Dissociation constants, 5: calculat,ions
by silver reductor and ceric sulphate involving, 9, 10, ll: primary and
(v), 308, 309: by sodium diethyl. secondary, 8: table of (acids and
dithiocarbamate (c), 666: by sodium bases), 7: true or thermodynamic, 6.
thiosulphate (v), 343; (p), 712: in Distribution coefficient, 140, 141 : method,
brass, 545, 557: in copper ore (v), 140.
344: in nickel silver, 563: in silver Dithiol, 663.
coinage alloy, 565: in steel, 578. Dithizone, 664, 665.
Copper-nickel alloy, analysis of (e), 526. Dolomite, analysis of, 582.
Coprecipitation, 109. Draining time, 196.
Coulomb, 129. Drierite, 506.
Counter e.m.f., 130. Dropping mercury electrode (cathode), 734,
Counter ions, 106. 735, 736: advantages of, 736:.
Cresol red, 55. assembly, 750-5.
Crucibles. 179: Gooch, 210: ignition of, Drying agents, 181: comparative effici.
212, 213: Main-Smith, 218, 219: encyof, 182.
micro, 820, 828: Munroe, 213: Drying of precipitates, 217.
Nebauer, 820: perforated screens for, Dubosq-type colorimeter, 608: use of, 610.
222: porcelain, 179: porous-porce. Duplication method, 603, 607.
lain filter, 214: Rose, 466: sintered
glass filter, 213: Vitreosil filtering, Elecdropode, 757.
213: with interior.fitting serrated lid, Electric ovens, 186.
218: with permanent porous plates, Electrical units, 128.
213: with permanent porous plates, Electrification due to wiping, 161, 816.
cleaning of, 214. Electro-analysis, theory of, 128, 528.
Crushing and grinding, 189. Electrochemical equivalent, 129: series,
Cubic centimetre. 191, 873. 80.
Cupferron, ll9. Electrode potentials, 78: change of, during
Cupron, 121. titration of an oxidant and a reduc.
Cuprous oxide, 803. tant, 87: table of standard, 80.
lnaex
Electrodes: antimony, 683: auxiliary, Ferric alum indicator, 257.
527,528; calornel, 676-8, 696; glass, Ferric iron, D. of: by mercurous per-
684-6: hydrogen, 79, 675, 676; chlorate (v), 388: by potassium
quinhydrone, 681-3: silver-silver dlchromate, after reduction (v) 295-
chloride, 678. by sodium thiosulphate (v), 356: by
Electrodes for electrolytic determinations, titanous salts (v), 316: by vanadous
510-18: Classen, 510, 511: Fisher, sulphate (v), 324 (see also under Iron)_
513, 514: mercury cathode, 514, Ferric iron, reduction of : by amalgamated
515: paddle.shaped, 512, 513 : zinc, 222, 225, 277: by cadmium
Sand's original, 512: Sand's modified, reductor, 223: by hydrogen sulphide,
513: use and care of, 516: 'Vinckler, 280 : by .Jones reductor, 222, 277 : by
513. liquid amalgams, 317: by silver
Electrode reactions, 131. reduct or, 224: by stannous chloride,
Electrode vessel, 515. 276: by sulphurous acid, 280: by
Electrolysis: controlled potential, 136, zinc and sulphuric acid, 281.
527: internal, 138: rapid, 135, 519 : Ferricyanides, D. of: by sodium thio
slow, 135, 519: unit, 509; com- sulphate (v), 356.
mercial forms of, 509, 510. Ferroin, 303 (see o-Phenanthroline ferrous
Electrolytic determinations, 509_ sulphate).
Electrolytic dissociation, 1. Ferrous ammonium sulphate (Mohr's salt) :
Electrolytes, weak, 3. purification of, 271.
Electrolytic separation of metals, 134, 526 : Ferrous iron, D. of : by ceric sulphate (v),
with controlled cathode potential, 307, 308; (m), 839: by manganic
136, 527, 545. sulphate (v), 313: by potassium di-
Elementary analysis, samples and solutions chromate (v), 295: by potassium
I for, 854: schemes of, 876. iodate (v), 366: by potassium
E.m.f., of voltaic cells, 81: polarisation, permanganate (v), 276 (see also under
130. Iron).
Emission spectrography, 96. Ferrous and ferric iron in an ore, D. of :
Emulsoids, 105, 106. (v),296.
End points, 35, 47: in neutralisation re- Filter beakers, 826: use of, 827.
actions, 690, 708, 725; indicators for, Filter mats, 210.
68: in oxidation-reduction reactions, Filter papers, 207: folding of, 209:
691, 709, 710; indicators for, 90: in incineration of, 217, 219: macerated,
precipitation and complex-formation 210, 410: quantitative, table of,
reactions, 72-7, 691, 709, 729. 208.
Eosin, 76, 253. Filter sticks, 823, 826: forceps for, 825.
Equilibrium constants, 4: of oxidation- Filter tubes, 827: use of, 828.
reduction reactions, 83. Filters, 598; see Light Filters_
Equivalence point, 35, 47. Filtration, 207: accelerated, 209: ap
Equivalent system, advantages of, 43. paratus for quantitative, micro, 823-
Equivalent weights, 36: of acids, 37: of 9: technique of, 209, 216: with
bases, 37: of oxidising agents and of filter crucibles, 211-15: with filter
reducing agents, 37, 38, 41, 42, 44: paper, 208-10, 216.
of salts, 37. Flame photometry, 94: spectrophoto-
Erioglaucine, 30, 304. meter, 95.
Eriochrome Black T, 387. Flasks, conical (Erlenmeyer), 178 : micro-,
Erio green, 301, 304. 820: standardised, 195.
Errors: absolute, 142: classification of, Flocculation values, 107.
143: curve, 144: determinate or Fluorescein, 76, 252.
constant, 143: indeterminate or Fluorides, D. of: as calcium fluoride (g),
accidental, 144 : in quantitative 494, 495: as lead chlorofluoride (g),
analysis, 142: in weighing, 161: 494; (v), 261: as triphenyl tin
minimisation of, 146: probable, 144 : fluoride (g), 494, 495: by thorium
relative, 142: titration, 35. nitrate (v), 393.
p-Ethoxychrysoidine, 360, 370. Fluorimeter, 635.
Ethyl ether, extractions with, 140: Fluorimetry, 599, 635: apparatus for, 636.
peroxide in, 517. Fluosilicates, D. of: (g), 505: by thorium
Ethylenediamine, 125: use in separation nitrate (v), 393.
of copper and mercury, 126. Fluxes, 190.
, Explosion and combustion, methods of Formates, D. of: by potassium per.
analysis, 804. manganate (v), 289.
External indicators, 93, 292, 379. Fractional combustion: of gases, 770:
Extinction, 601. pipette, 793.
Extinction coefficient, 600, 601: mole- Funnels, 179, 208: analytical, 208, 209 :
cular, 600, 601: specific, 600, 601. Buchner, 184: sintered glass, 184:
Extraction: of solid mixtures by solvents, "slit-sieve," 184.
139: of solutions by solvents, 140. a-Furildioxime, ll8.
Furoic acid, 237.
Faraday, 129: laws of, 128. Fusions: with potassium pyrosulphate,
FelSIJar, analysisor,
588. 587: with sodium carbonate, 588.
910 Index
Gas analysis: apparatus employed in, 786: burette, 784: double absorp-
784: by explosion and combustion tion pipette, 786: explosion pipette,
methods, 804: exercises in, 806: 787, 804: modified burette, 789:
general discussion, 778: gravimetric pipette for solid reagents, 785:
methods, 778: physical methods, simple gas pipette, 784: slew com-
778: titration methods, 778: volu- bustion pipette, 787.
metric methods, 778, 808_ Hempel-Winckler gas burette, 784.
Gas measuring vessels, calibration of, 783. Hexamethylenetetramine, 455.
Gas volumes: automatic correction to Hot plates, 186.
~.T.P., 782: correction for tempera- Hydrazine, D. of: by potassium iodate
ture and pressure, 781. (v),365.
Gas volumeter, Lunge's, 782. Hydrazine hydrate, 455, 456.
Gas volumetric analysis, 808. Hydrochloric acid: composition of con-
Gauss's method of double weighing, 160. stant b.p., 227: preparation of
Gelatin, as maximum suppressor in constant b.p. acid, 228: preparation
polarography, 755. of O'lN-, 229: standa.rdisation of, by
Gels, 106. anhydrous sodium carbonate (v),
German silver, 562. 229; by borax (v), 231; by an iodo-
Germanium in steel, D. of : as dioxide (g), metric mcthod (v), 330; by a gravi-
580_ metric method (as silver chloride),
Glass electrode, 684: determinations 400: HCI content of concentrated
with, 685: limitations of, 685, 686. acid (v), 258.
Glassware, 178: cleaning of, 193. Hydrofiuosilicate, D. of: by thorium
Gold, D. of: as metal (g), 445-7. nitrate (v), 393.
Gooch crucibles, 211: asbestos for, 210: Hydrogen electrode, 79, 675: advantages
heating of, 212: preparation of, 211 : of, 681: Hildebrand bell type, 676 :
rubber sleeves for, 211, 212: vitreosil limitations of, 68l: Lindsev, 676:
(silica), 210. preparation and use of, 675 . .
Graduated cylinders, 203. Hydrogen ion colorimeter, 640.
Gram, 16. Hydrogen ion concentration, 23: in
Gravimetric analysis, 397: calculations of, buffer solutions, 30, 868: in hydro-
396: forms in which elements and lysed salts, 27-30, 66-8 (see also
radicals are commonly precipitated, under pH).
101: micro-, 814: systematic, general Hydrogen ion exponent, 233 (see also
discussion of, 419: technique of, under pH).
206: theory of, 100. Hydrogen peroxide, D. of: by ceric
Gravimetric separations, simple: alumin- sulphate (v), 311: by manganic
ium and chromium, 550: calcium sulphate (v), 313: by potassium
and barium, 552: calcium and iodate (v), 365: by nitrometer or gas
magnesium, 551, 585, 587: calcium volumeter (gv), 810, 811: by potas-
and strontium, 552 : calcium, sium permanganate (v), 283: by
strontium and barium, 553: iron and sodium thiosulphate (v), 348.
aluminium, 548, 549, 589: iron and Hydrogen sulphide: D. of, (v), 355:
chromium, 549, 550: manganese and precipitations with, 113: reductions
zinc, 551: nickel and zinc, 551: with,280.
sodium and potassium, 554, 590. Hydrolysed salts, titration of, 66.
Greases for glass stopcocks, 200. Hydrolysis, 26: degree of, 27: of salts, 25.
Greek alphabet, 875. .< Hydrolysis constant, 27: and degree of'
Ground solution, 734. hydrolysis, 27-30.
Gun metal, analysis of, 561. Hydroxides, precipitations at controlled
pH,115.
Half-wave potentials, 739, 741: of the Hydroxylamine, D. of: by potassium
cadmium ion in N-potassium chloride, bromate (v), 375.
D. of, 762: of the zinc and manganese p-Hydroxyphenylarsonic acid, 123, 124.
ions in X-potassium chloride, D. of, 8-Hydroxyquinaldine, 126, 467: prepara- . "
764. tion of, 126.
Halides, D. in admixture: by adsorption 8-Hydroxyquinoline, 119: determination
indicators (v), 255: by indirect of metals by, 371: precipitations
method (v), 255. with,120.
Hardness of water, 382-7: degrees of, Hypochiorites, D. of: (v), 350: as silver
383: D. of permanent, by soap chloride (g), 496.
solution (v), 384; by sodium carbon- Hypophosphites, D. of: as
ate (v), 386: D. of temporary, 385 : MgNH.PO.,6H 2 0 or as magnesium
D. of total, by Clark's method, 383; pyrophosphate (g), 501: by mercuric
by "didiette" or Trilon B method chloride as mercurous chloride (g),
(v), 386; by soap solution (v), 384 : 501.
table of, 385. Hyposulphites, D. of: by thiocyanate
Heating apparatus, 185. solution (v), 260.
Hehner cylinders, 608.
Hempel's apparatus, 784, 787: absorption Ignition of crucibles, 212, 213: of
pipette for fuming sulphuric acid, precipitates, 217.
Index 911
Ilkovic equation, 738. Iron and titanium in admixture, D. of, 321.
Incineration of .filter paper, apart from the Isopropyl ether. extraction with, 140.
precipitate, 219: in the presence of I.S.W.G., inches and millimetres, 875.
the precipitate, 219.
Indicator electrodes, 688: dropping mer- Jones reductor, 222, 277: applications and
cury, 734-6: rotating micro, 736. limitations of, 278, 279: preparation
Indicators, 47: acid-base, 47: adsorption, of, 278.
74, 251: apparent dissociation con- Journals of analytical chemistry, 850.
stant of, 49, 51: choice in neutralisa-
tion reactions, 68: colour change Karl Fischer reagent, 698: apparatus and
intcrva1 of, 47: colour changes and experimental details for titrations
pH ranges of certain, 52: external, with, 701-5: preparation of, 698:
93, 292: in oxidation-reduction some applications of, 706-8: stand-
titrations, 90: in precipitation re- ardisation of, 699-701.
actions, 72: ionisation constants of, Kilogram, international prototype, 153,
48: mixed, 55: neutralisation, 47 : 873.
internal oxidation-reduction, 90, 92 : Kjeldahl-Gunning process, 249.
preparation of solutions of, 53: Kjeldahl's method for nitrogen, 248 .
. screened, 56: theory of action of,
47-51: universal or multiplerange, Lambert's law, 599.
56. Lawrence Smith method, 591.
Internal electrolysis, 138. Lead amalgam, preparation of, 321: use
International prototype kilogram, 153. of, 321.
Iodates, D. of: as silver iodide (g), 497. Lead, D. of: as chromate (g), 420, 421 :
Iodides, D. of: as palladous iodide (g), as dioxide (e), 520: as iodate (g),
493: as silver iodide (g), 493: by 420, 422; (v), 422: as molybdate
potassium iodate (v), 361: by silver (g), 420, 421: as salicylaldoximate
nitrate (v), 254: by Volhard's (g), 420, 422: as sulphide (c), 664,
method, 259. 665: as sulphate (g), 420: by
10dometric method for standardising acids, dithizone (c), 664, 665: by sodium
330. 'thiosulphate (v), 347: in brass, 547,
Iodometry and iodimetry, 328: detection 557: in nickel silver, 562: in steel,
of end point in, 330: general dis- 579: in tartaric acid (c), 665.
cussion of, 329. Lead dioxide, analysis of (v), 346, 364.
Iodine, purification by sublimation, 185. Liebig's method for cyanide, (v), 263.
Iodine monochloride solution, preparation Light filters, 598, 614: choice of, 615, 616.
of,366. Limestone or dolomite, analysis of, 582.
Iodine solution: oxidising properties of, Limiting cathode potential, 529 (see also
328: preparation of O'lN-; 339,340 : Controlled potential electro-analysis).
standardisation of, by anhydrous Limiting current, with dropping mercury
sodium thiosulphate, 342; by arseni- cathode, 736, 739: factors affecting,
ous oxide, 341; by standard sodium 737.
thiosulphate solution, 343, (p) 711. Liquid capacity, measures of : apothecaries
Ion-electron method, 39. (British), 874: apothecaries (U.S.A.),
Ionic equations, for calculation of equiva- 874: Imperial or British, 273: U.S.,
lent weights, 42. 874.
Ionic product of water, 22: table at Literature of analytical chemistry, 845.
various temperatures, 23. Lithium, D. of: as sulphate (g), 490: in
Ionic strength, 6. admixture with sodium and potas-
Ionisation constants of acids, 5: table of, sium, 490.
7. Litmus, 54.
Iron, D. of : as ferric oxide (g), 407-9; by Litre, 191, 873.
basic benzoate method, 410; by Logarithms: five figure, 886 : . four-figure,
cupferron, 455, 457; by hexa- 884.
methylenetetramine, 455, 456; by Lovibond comparator, 639, 640.
hydrazine hydrate, 455, 456; by Lubricants for glass stopcocks, 200.
potassium cyanate, 455: as oxinate Lunge gas voll1meter, 782: nitrometer,
(g), 456 : by o-phenanthroline method 808.
(c), 646, 647: by thiocyanate (c),
645, 646 : by thioglycollic acid Macerated filter-paper, 210, 410.
method (c), 646, 647: by vanadous Magnesia mixture, 435.
(II) sulphate (v), 324: in brass, 558 : Magnesium, D. of: as l\'[gNH.PO.,6H.O
in felspar, 589: in ferric ammonium (g), 414, 416; (m), 835: as 2-
sulphate (v), 281, 295, 324: in lime- methyloxinate (g), 481: as oxinate
stone or dolomite, 586: in nickel (g), 373, 481: as pyrophosphate
silver, 563: total, in an iron ore, by (g), 414, 416: by oxine (v), 373:
ceric sulphate (v), 307; by potassium by titan yellow (c), 668, 669: in
dichromate (v), 296; by potassium an aluminium alloy, 581: in fel-
permanganate (v), 282; by titanous spar, 590: in limestone or dolomite,
chloride or sulphate (v), 316. 585, 587: in portland cement,
lrOll ware, 179: wire, A.R., 271. 594.
912 Index
Main-Smith crucible, 218, 219. syringe pipettes, 834 : titration
Manganese, D. of: as MnNH,PO"H 2 0 vessels, 835; cleaning of, 835:
(g), 468: as pyrophosphate (g), 468': transfer pipettes, 833, 834: volu-
by periodate method (c), 648: by metri() flasks, 829: wash bottles,
potassium perrnanganate in pyro- 816: wash-out pipettes, 833: water-
phosphate solution (p), 713-14: in baths, 821: weighing bottles, 821,
steel, by bismuth ate method (v), 287 ; 822: weighing" piggy," 822.
by persulphate-arsenite method (v), Micro-b.alances, 814: precautions in
289; by periodate method (e), 648; weIghing with, 816: setting up of,
by potassium permanganate (p), 714. 815. .
Manganese dioxide in pyrolusite, D. of: Micro-gra17imetric and micro-17olumetric
by nitrometer (gv), 8Il: by potas- analysis, 814: general discussion of,
sium dichromate (v), 299: by potas- 814.
sium iodate (v), 364; by potassium Micro-gra17imetric determinations, simple,
permanganate (v), 285; (p), 714: by 835.
sodium thiosulphate (v), 345, 346. Micro-volumetric determinations, simple,
Manganic sulphate solution: applications 837.
of, 313: oxidising properties of, 312 : Migration current, 737.
preparation and standardisation of, Millilitre, 191, 873.
312. Mobilities, ionic, 718: table of, at infinite
Mannitol, 246. dilution at 25 C., 719.
Mass action law, 3: applications to Mohr procedure: experimental details for,
solutions of electrolytes, 5. 251, 252: theory of, 72. .
Maxima in polarography, 739. Molar solution, 36.
Maximum suppressors, 744, 755. MolybdenUm, D. of: as lead molybdate
Mean deviation, 142: relative, 142. (g), 439, 440: as molybdyl oxinate
Me,asuring cy1jnuers, 203. (g), 439, 441; (v), 439: by a-benzoin,
Measuring flasks, 193 (see also Volumetric oxime (g), 439, 440: by Jones
flasks). reduc1,or and potassium permanganate
Meniscus, reading position of, 199,200. (v), 31.9: by silver reductor and eerie
Meniscus correction, 783: double, for sulphttte (v), 309: by thiocyanate
water and mercury, 783, 784. method (c), 653, 654: in ~teel, 574,
Mercuric nitrate, standard solution of, 266. (c),654.
Mercurous nitrate: reagent, 454: standard Moroney evaporator, 187.
solution of, 253. Mortar: Inullite, 189: percussion, 189:
Mercurous perchlorate, standard solution synthEltic sapphire, 189.
of, 254, 388. Muffle furnace, 186.
Mercury: cathode, 514: density at Multiple-range indicators, 56, 638.
various temperatures, 781 : poisonous Munroe crucible, 213.
character of, 780: spilled, collection
of, 781. Naphthol Blue Black, 360, 368, 370.
Mercury, D. of: as mercury zinc thio- a-Naphtho6.avone, 370.
cyanate (g), 423, 424: as para- a-Naphtholphthalein, 54.
periodate (g), 423; (v), 424: as Neo-cupferron, 119.
sulphide (g), 423, 424: by ethylene- Nephelometers, 635.
diamine (g), 423, 424: by potassium Nephelometry, 599, 635: instruments for.
iodate (v), 363: in aqua regia ()36.
solution, 425. Nessler's rE)agent, 643.
Meta-cresol purple, 55. Nessler tubes, 605: stand for, 606.
Methyl orange, 53, 54: -xylene cyanol FF, Nesslerimeter, B.D.H.-Lovibond, 606, 640.
55. Neutralisation curves, 57: of a polybasic
a-Methyloxine, 126: preparation of, 126. acid with a strong base, 64: of a.
Methyl red, 54. strong acid and a strong base, 57: of
Methyl yellow, 55. a weak acid and a strong base, 60:
Metric and other units, comparison of, of a weak acid and a weak base, 63 :
873-5. of a weak base and a strong acid, 62.
Micro-analysis, miscellaneous apparatus Neutralisation reactions, 36, 690, 708, 725 :
for, 816. choice of indicators in, 68.
Micro apparatus for quantitative filtration, Neutral red, 55.
823 : apparatus for volumetric Nickel, D. of: as metal (e), 458, 523: by
analysis, 816: beakers, 820; stand dicyandiamidine (g), 458, 459; (v).
for, 824: burettes, 830: burners, 458, 459: by dimethylglyoxime (c),
820, 821 : centrifuges, 823: crucibles, 654,655; (g), 417,457; (m), 837 : by
820, 828: desiccators, 816-20: oxine (v), 374: by potassium cyanide
evaporating basins or dishes, 820: (v), 264: by pyridine-ammonium
filters, 820: filter-beakers, 826; use thiocyanate method (g), 457, 458;
of, 827: filter-sticks, 823; stand for, (v), 261: by salicylaldoxime (g), 457,
824; use of, 825: filter-tubes, 827; 458: in nickel silver, 563: in nickel
use of, 828: flasks, 820: forceps, steel )), 655; (g), 418, 459, 460; (v),
825: metal block, 817, 818: Nebauer 265, 459: in a silver coinage alloy,
crucibles, 820: pipettes, 832: safety 566. ->
Index 913
Nickel silver, analysis of, 562. Peptisation, 106, 107.
Nickel ware, 179. Perchiorates, D. of: as potassium per-
Nitrates, D. of: as nitron nitrate (g), 505 : chlorate (g), 496, 497: as silver
by gas volumeter (gv), 809: by chloride (g), 496.
nitrometer (gvt, 808: in Chili salt Perchloric acid: explosive dangers of,
petre (v), 248. 503: use in D. of silicates, 503: use
Nitrites, D. of : by ceric sulphate (v), 308 : . III D. of sulphur in steel, 569, 572.
by chloramineT (v), 377: by a Penodates, D. of: as silver iodide (g)
naphthylamine and sulphanilic acid 497. '
(c), 644: by N.(l.naphthyl).ethylene. Peroxides, D. of: by nitrometer or gas
diamine and sulphanilic acid (c), 645 : volumeter (gv), 810: by potassium
by potassium permanganate (v), 285. iodate (v), 286.
Nitrogen, D. by Kjeldahl's method (v), Persulphates, D. of: by potassium per.
248. manganate (v), 286.
Nitron, 123. pH, 23, 674: calculations involving, 24:
a-Nitroso-,B-naphthol, 122. D. of, by antimony electrode, 683;
Nitroso-R-salt, 655. by colorimetric methods, 638; by
Nitrous acid: removal of, 518 (see also glass electrode, 685; by hydrogen
under Nitrites). electrode, 675; by quinhydrone
Normal solutions, 36, 37: preparation of, electrode, 681: meters, 686-8: of
45. buffer solutions, 868: standards for,
Normality, 43. 674, 868.
. Note-book, 397. o-Phenanthroline, 646, 647 .
N-Phenylanthranilic acid, 293, 303. o-Phenanthroline ferrous sulphate, 90, 272,
293, 303.
Ohm, 128: law of, 128. Phenolphthalein, 54.
Opacity, 600. Phenol red, 55.
Optical density, 600, 601. Phenosafranine, 76.
Organic precipitants, 117. N-Phenylanthranilic acid, 293, 303.
Orsat apparatus, 792. Phenylthiohydantoic acid, 122.
Orsat-Lunge apparatus, 792: use of, 792- Phosphates, D. of: as MgNH 4P0 4 ,6H 20
5. or as magnesium pyrophosphate (g),
Ortho-phenanthroline ferrous sulphate (see 499; via ammonium phosphomolyb.
o-Phenanthroline ferrous sulphate). , date (g), 499, 500: as molybdyl
Overvoltage, 132. oxinate via ammonium phospho
Osmic acid solution, 303. molybdate (g), 380, 381: as am
Oxalates, D. of : as calcium carbonate (g), monium phosphomolybdate (v), 380-
502: as calcium oxide (g), 502: as 1.
calcium oxalate monohydrate (g), Phosphites, D. of: as MgNH 4 P0 4 ,6H 2 0
502; ,(m), 837: by ceric sulphate (v), or as magnesium pyrophosphate (g),
307: by manganic sulphate (v), 313 : 501 : by mercuric chloride as
by potassium permanganate (v), 273. mercurous chloride (g), 501.
Oxidants, 39: equivalent weights of, 41 : Phosphor bronze, 560: analysis of, 562.
table of, 42. Phosphoric acid, action on indicators, 65,
Oxidation, 38: number method, 41. 66: D. in commercial acid (v), 245 :
Oxidation potentials, 82: calculation of, neutralisation of, 64.
83: table of standard, 82. Phosphorus, D. of: (v) 380 (see Phos-
Oxidation-reduction cells, 81. phates): in phosphor bronze, 562: in
Oxidation-reduction curve, 87. steel, 566.
Oxidation-reduction indicators, 90: table Photo-cells, 611, 612.
of,92. Photo-electric colorimeters, 611: com
Oxidation-reduction reactions, 36, 37: mercial forms of, 616-25; onecell
equilibrium constants of, 83: theory types, 616-20; twocell types, 620-5.
of,77. Photo-electric filter photometer method,
Oxidation-reduction titrations: change of 604, 611.
potential during, 87: indicators for Photo-emissive cells, 611.
detection of end points in, 90-3: Pipettes: absorption (Shepherd), 794:
potentiometric methods for determin. calibration of, 196: fractional com
ing end points in, 93, 691, 709. bustion, 793 : graduated, 195 :
Oxidising agents, 41: table of, 42. Hempel explosion, 787, 804: in gas
Oxine, 119: determination of metals by analysis, 784-7, 794: Lunge-Rey,
(v), 371 : precipitations with, 120. 203: micro, 832: safety syringe,
834: slow combustion, 787, 793:
Palladium, D. of: as metal via palladous slow combustion (Ambler), 806: slow
cyanide (g), 444: by dimethyl. combustion (Dennis), 805: slow
glyoxime (g), 444, 445: by 1 : 2-cyclo. combustion (improved), 806: stand
hexanedione dioxime (g), 444, 445. ardised, 197: tolerances of, 197:
para-Hydroxyphenylarsonic acid, 123, 475. transfer, 95: washout, 833.
Parallax, errors due to, 200. Platinum apparatus, 179: care and use of,
Parallel determinations, 146. 220: cleaning and preservation of,
Pa.~ition coefficient, 140, 141. 221.
914 Index
Platinum, D. of : as element, by reduction Potassium iodate solution: for standard-
with formic acid (g), 443: as element isation of acids, 330: indicators for.
via ammonium chloroplatinate (g), 360: oxidising properties of, 358,
443,444. 359: preparation of 0'025M-, 361.
Poggendorff's compensation method, 678. Potassium iodate and potassium iodide.
Point of rest, 155. standard solution of, 330: standard-
Polarisation e.m.f., 130. isation of strong acids with, 330.
Polarised electrode systems, 692, 710. Potassium iodide-starch paper, preparation
Polarised metallic electrodes, 692. of,349.
Policeman, 180, 827. Potassium permanganate solution: appli-
Polarograms, 734: of air-saturated potas- cations in alkaline solution, 269:
sium chloride solution, 743. discussion of substances for standard-
Polarograph, 734: ancillary equipment isation, 270: oxidising properties of,
for, 750-5: commercial manual non- 268: permanence of, 275: prepara-
recording, 755-7 : commercial record- tion of O'lN-, 271: reduction of,
ing, 758-62: home-made, 746-50. 468: standardisation of, by arsenious
Polarographic analysis: ancillary equip- oxide, 272; by ferrous ammonium
ment for, 750-5, 761 : basic apparatus sulphate, 275; by metallic iron, 274 ;
for, 734, 735: cells for, 753-4: by oxalic acid, 275; by potassium
concentration range for, 743: in- ferro cyanide (anhydrous), 274; by
fluence of dissolved oxygen, 743, 744, potassium tetroxalate, 275; by
766: D. of cadmium in solution by, sodium oxalate, 273.
765: D. of magnesium in solution by, Potassium tetroxalate,. 238.
766. Potassium thiocyanate solution: prepara-
Polarographic wave, 736: equation of, 741. tion of O'lN-, 256: standardisation
Polarography: evaluation of quantitative of, 257.
results, 745-6: general introduction Potassium titanyl oxalate, 650.
to, 734-7: quantitative technique of, Potential mediators, 92.
743-5 : theoretical principles of, Potentials: decomposition, 129, 130:
737-43. electrode, 78: oxidation, 82, 83:
Porcelain apparatus, 179. standard or normal, 79, 80: standard
Porous-porcelain filter-crucibles, 214 : oxidation, 82.
cleaning of, 214, 215: micro, 820, Potentiometer, 678: Tinsley general-
828; use of, 829. utility, 679.
Portland cement, analysis of, 592. Potentiometric titrations, 36, 93, 673:-
Post-precipitation, 11 O. differential method, 690: theory of,
Potassium, D. of: as chloroplatinate (g), 93-4, 673-5.
484,486,487: as K.Na[Co(N02)6lH.O Potentiometric titrations, experimental
(g), 485, 488; (v), 388, 485, 499: as details for classical method, 688-91 :
perchlorate (g), 484, 487; (v), 486, neutra.lisation reactions, 690, 708:
489: as sulphate (g), 485: by eerie oxidation-reduction reactions, 691,
sulphate (v), 388: in admixture with 709: precipitation reactions, 691, 709.
sodium (g), 488: in admixture with Potentiometric titrations, simplified elec-
sodium and lithium (g), 484, 490: in trode systems and methods, 692-8:
felspar, 590. bimetallic system, 693: dead stop
Potassium bi-iodate, preparation of, 238 : technique, 692': commcrcial appara- "
use in micro-analysis, 838. tus for, 689, 694-8.
Potassium bitartrate, 238. Precipitants, organic, 117.
Potassium bromate solution: indicators Precipitate: drying and ignition of, 217 :
for, 368: oxidising properties of, effect of acids upon the solubility of,
368: preparation of O'lN-, 369. 20: effect of solvent upon the solu-
Potassium cyanate, 453. bility of, 22: effect of temperature
Potassium cyanide: action upon indica- upon the solubility of, 21 : formation,
tors, 66: standard solution of, 264: 108: ignition of, 217-24: incinera-
titration with strong acids, 66. tion of filter-paper apart from the,
Potassium dichromate solution: external 219: incineration of the filter-paper
indicators for, 292: internal indica- in presence of, 217: purity of, 109,
tors for, 293: oxidising properties of, washing of, 111,209,215.
292: preparation of O'lN-, 294: Precipitation, 112, 206: and supersatura-
purification of, 294: reduction, of, tion, 108: completeness of, 14:
453: standardisation of, by iron, conditions of, 110: discussion of.
294; by ferrous ammonium 13ulphate, 206: factors determining a successful
294. analysis by, 100: fractional, 17, 112 :
Potassium ferricyanide, as external indica- of hydroxides, 113: of sulphides,
tor, 293, 295: standard solution of, 113 : practical points concerning, 206_
715. Precipitation methods, 100.
Potassium ferrocyanide, anhydrous, pre- Precipitation reactions, 36, 37, 697, 709,
paration of, 305. 729: theory of, 69.
Potassium hydrogen phthalate: as pH Precision, 143.
standard, 674, 868: as standard Pregl drying block, 819, 821, 828: micro-
substance, 236. desiccator, 818.
Index 915
Pressure bottle, 347. Separations: by miscellaneous physical
Preventive solution, 269. methods, 139 : by precipitation
Primary standards, requirements of, 46. methods, 112: electrolytic, 134, 136,
Probable error, 144. 526, 545: simple gravimetric, 548.
Probability curve, 144. Shepherd apparatus, 794.
n-Propylarsonic acid, 123. Significant figures, 147.
Protective colloid, 107. Silica apparatus, 179.
Purification of substances, 184. Silica, D. of: as molybdenum blue (c),
Pyridine, 124. 669: as quinoline silicomolybdate
Pyrogallol, 125: in gas analysis, 802. (v), 390: in aluminium alloys, 582 :
Pyrolusite (see Manganese dioxide). in felspar, 589: in limestone or
dolomite, 582: in insoluble silicates
Quartz (Vitreosil) filtering-crucibles, 213. (g), 502, 504: in portland cement,
Quinaldinic acid, 124: recovery of, 125. 593: in soluble silicates (g), 502,
Quinhydrone electrode, 681: a.dvantages 503.
of, 682: disadva.ntages of, 681, 682. Silicon, D. of: in an aluminium alloy,
582: in steel, 568.
Radiator, 187. Silver apparatus, 179.
Reagents, 182: a.nalytical, 183; quality Silver coinage alloy, analysis of, 565.
of, 183; use of, 183: saturated Silver, D. of : as chloride (g), 422, 423: as
solutions of, 883. metal (e), 524: by OINammonium
Recording of results, 397. thiocyanate (v), 256: in alloys (v),
Recrystallisation, purification of solids by, 257: in silver coinage alloys, 565.
184. Silver nitrate solution: preparation of
Red lead, analysis of (v), 285, 346. OIN, 251: standardisation of, with
Redox processes, 39. sodium chloride and potassium
Reducing agents, 38, 39: equivalent chromate indicator, 251 ; with sodium
weights of, 42: table of, 42. chloride and adsorption indicator,
Reduction, 39: by amalgamated zinc, 222, 251.
,224, 277, 317: by cadmium powder, Silver reductor, 224: preparation of silver
223': by ch\omous salts, 325: by for, 224: use of, 225, 296, 309.
lead amalgam, 321: by liquid Silver-silver chloride electrode, 678.
amalgams, 317: by liquid zinc Simple gravimetric analysis, 398: micro,
amalgam, 319: by silver powder, 835.
224 ~ by titanous salts, 314: by Sintered-glass crucibles, 213: advantages
vanadous salts, 322: of ferric salts, of, 213.
276. Snipe feather, 827.
Beduction of ferric salts: by amalgamated Soap solution, preparation of standard,
. zinc spirals, 225: by hydrogen 383.
sulphide, 280: by Jones reductor, Soda lime, 506. ..
222, 277: by liquid amalgams, 317 : Sodium anthraquinone-,B-sulphonate, 802.
by silver reductor, 224, 296, 309: by Sodium bismuthate, 287.
stannous chloride, 276: by sulphur Sodium carbonate: as standard substance,
ous acid, 280: by zinc and sulphuric 229: choice of indicators for, 67:
acid,281. content of washing soda, 239:,
Relative mean deviation, 142. preparation of pure, 229: titration
Residual' current, 737, 739. with strong acids, 67.
Residual process, 256, Sodium cobaltinitrite reagent, 478, 488.
Rest point, 155. Sodium, D. of: as magnesium uranyl
Rhodamine 6G, 76. acetate (g), 482, 483: as zinc uranyl
Rhodizonic acid, sodium salt, 267. acetate (g), 482, 483: as magnesium
Rider, 151. or zinc uranyl acetate (v), 387: as
Rose crucible, 466, sulphate (g), 482: in felspar, 590.
Sodium diethyldithiocarbamate, 666.
Salicylaldoxime, 121. Sodium diphenylamine sulphonate, 293,.
Salt bridge, 675, 722. ." 294.
Salt effect, 17. Sodium hydroxide solution: preparation
Salts, 3. of carbonate free, 233-5 : preparation
Samples, crushing and grinding of, 189: of OlN., 234, 235: standardisation
solution of, 189: weighing of, 158 of, by standard acid, 235; by potas
(see also Analysed samples). sium hydrogen phthalate, 236.
Sampling of solids, 187: of gases, 779-80. Sodium hyposulphite, 802: with sodium
Saturated solutions of some reagents, 883, anthraquinone. ,Bsulphonate, 802.
Schemes of study, 876, 878. Sodium peroxide, analysis of (v), 284.
Screened indicators, 56. Sodium rhodizonate, 267.
Screens, perforated, for crucibles, 222. Sodium starch glycollate, 331 : preparation
Selenium, D. of: as element (g), 442, 443 : of, 332: preparation of indicator
by potassium permanganate (v), 290; solution, 332.
by sodium thiosulphate (v), 291. Sodium thiosulphate, anhydrous, as a
Selenium and tellurium in admixture, D. primary standard, 334: preparation
,pf: (g), 441, 442, 443; (v), 291. of,334 .
.;
~Hi Index
Sodium thiosulphate solution : preparation 403; with agar agar as coagulant,
of OlN., 333, 334: preparation of 404; with picric acid as coagulllnt,
OOlN, 838: stability of, 333: 498: by benzidine sulphate method
standardisation of, by eerie sulphate, (c), 669, 670.
339: by copper, 337; (m), 838: by Sulphatoceric acid, 301.
potassium bromate, 335: by potas Sulphide ion concentration, calculation of,
sium dichromate, 336; (p), 711: by in a saturated aqueous solution, 9, 10.
potassium iodate, 334: by potassium Sulphides, D. of: as barium sulphate (g),
permanganate, 339; (p), 711: by 498: by iodine (v), 355.
pure iodine, 338: by standard iodine Sulphides, precipitation of, 113.
solution, 338; (p),711. Sulphites, D. of: as barium sulphate (g),
Sofnolite, 506. 498: by iodine (v), 354.
Sol, 106. Sulphonephthaleins, 55.
Solder, analysis of, 563, 564. Sulphur, D. of: in mineral sulphides (g),
Solubilities of inorganic substances, at 407: in iron pyrites (g), dry process, .
various temperatures, table of, 866. 405; wet process, 405, 406: in steel,
Solubility product, 11, 16: calculations 567.
involving, 14, 15: principle, 12: Sulphuric acid, D. of : in the concentrated
principle, limitations of, 15. acid (v), 241: in oleum (v), 241.
Solution of sample, 189: experimental Sulphurous acid and sulphites, D. of: as
details for, 189-91. barium sulphate (g), 498: by iodine
Spectrograph, Hilger medium quartz, 96. (v), 354: reductions with, 280.
Spectrography, emission, 96-8. Supersaturation and precipitate formation,
Spectrophotometer, 598: method, 605. 108.
Spectrophotometry, 598, 599: theory of, Supporting electrolyte, 734, 737, 738.
599. Suspensoids, 105, 106.
8pectrophotometers, photo-electric : Beck Systematic gravimetric analysis, 419.
man, model B, 631: Beckman model
DU quartz, 633: Coleman universal, Tannin, 123.
model 14, 630: Hilger uvispek, 626 : Tare, 161: for micro-analysis, 816.
Unicam ultra-violet and visible, 628. Tartrazine, 257.
" Speedy-vap " beaker cover, 190. Tellurium, D. of: as dioxide (g), 442,
Standard series method, 603, 605. 443: as element (g), 442, 443: by.
Standard solutions, 35, 36: preparation of, ceric sulphate (v), 310: by potassium
45: storage of, 204. dichromate (v), 310: by potassium
8tandard substances for acidimetry and permanganate (v), 310: in mixtures
alkalimetry: adipic acid, 238: an- with selenium (g), 441; (v), 291.
hydrous sodium carbonate, 229: Temperature, standard, 192: correction
benzoic acid, 237: borax, 231: for I-litre volumetric flasks, 192.
constant b.p. hydrochloric acid, 228 : Test papers, 182.
furoic acid, 237: oxalic acid, 238: Thallium, D. of: as thaIIous chromate
potassium bi-iodate, 238: potassium (g), 477, 478: as thaIIous cobalti-
bi.tartrate, 238: potassium hydrogen nitrite (g), 477, 478: by potassium
phthalate, 236: potassium tetroxa- iodate (v), 366.
late, 238: sodium oxalate, 236: Thermionic valve titrimeters, commercial,
succinic acid, 237: sulphamic acid, 694-8: use of, 710, 711.
238. Thiocyanate and chloride in admixture, D.
Standard temperature, for volumetric glass- of: (v), 266.
ware, 192. Thiocyanate, D. of: as barium sulphate
Starch solution: disadvantages of, 331 : (g), 494: as cuprous thiocyanate (g),
preparation and use of, 331, 332: 493: as silver thiocyanate (g), 493 :
stability of, 332. by mercuric nitrate (v), 265: by
Steam-baths, 185. silver nitrate (v), 255.
Steam-ovens, 186. Thioglycollic acid, 646.
Steel, analysis of, 566. Thiosulphate, D. of: as barium sulphate
Stirring: in electrolytic determinations, (g), 498: by iodine (v), 388 (see
516, 528: magnetic, 528: rods, 180. also Sodium thiosulphate).
Stoichiometric point, 47. ' Thorium, D. of: as thoria via iodate (g),
Storage of solutions in volumetric analysis, 472; via oxalate, 471, 472; via
204. sebacate, 472.
strong acid, standardisation by an iodi- Thymolphthalein, 54.
metric method, 300. Tin, D. of: as dioxide (g), 437, 438: by
.Strontium, D. of : as oxide via oxalate (g), ammonium iodide procedure, 437,
479: as sulphate (g), 479. 561 : by thiostannate procedure, 556 :
Sublimation, purification of solids by, 185. by chloramine-T (v), 377: by cup-
Succinic acid, 237. ferron (g), 437, 438: by dithiol (c),
Sulphamic acid: for removal of nitrous 663, 664: by iodine (v), 352, 353,
acid, 518: purification of, 238. 354: by phenylarsonic acid (g), 437,
Sulphate, D. of: (v), 267: as barium 438: by potassium iodate (v), 363 :
sulphate (g), 401, 497; filter-crucible in foodstuffs and organic materials,
method, 403; filter-paper method, 663: in nickel silver, 562.
Index 917
Titanium, D. of: as titania (g) via cup manganate (v), 319: in steel, 572,
ferron complex, 474; via para- 651.
hydroxyphenylarsonic acid complex, Vanadous (vanadium, U) salts, reductions
474,475; via selenious acid complex, with,322. .
474, 475; via tannin an.d antipyrine Vanadous sulphate (VSO.): preparatlOn
complexes, 474: by cadmium re- of, 323: standardisation of, 324.
ductor and eerie sulphate (v), 223: Vapour pressure of water, table of, at
by hydrogen peroxide (c), 649: by various temperatures, 782.
Jones reductor and potassium per- Vinegar, D. of acetic acid content of (v),
manganate (v), 318: by liquid zinc 241.
amalgam and ferric ammonium sul- Vitreosil filtering-crucibles, 213.
phate (v). 320: by oxine (v), 374: in Volatilisation methods, 127.
felspar, 590: in steel, 576. Volhard procedure: applications of, 256,
Titan yellow, 668. 258, 259: theory of, 73.
Titanous chloride solution, preparation of, Volt, 129.
314: sulphate solution, preparation Voltaic cells, 81.
of, 315: standardisation of, by ferrous Voltamoscope, 755.
ammonium sulphate (v), 316; by Volumetric analysis: classification of re-
iron (v), 315. actions in, 36: conditions a reaction
Titanous salts, reducing properties of, 314. must fulfil for, 35: general dis-
Titration, 35: curves, 58, 59, 61, 63, 65, cussion of, 35: micro-, 815, 829.
67, 70, 88: error, 35: of borax with 837: storage and preservation of
a strong acid, 67: of potassium solutions in, 204: technique of, 191.
cyanide with a strong acid, 66: of Volumetric apparatus, 192: micro-, 829.
sodium carbonate with a strong acid, Volumetric flasks, 193: calibration of,
67. 194: micro-, 829: standardised,
Titration apparatus, commercial, 689, 195: tolerances of, 195.
694-8.
Titrations: arrperometric, 769: colori- Walpole technique for pH, 639.
metric, 607: conductometric, 718: Wash bottles, 177: micro-, 816.
displacement, 66, 728: potentio- Washing by decantation, 216.
metric, 93, 673: precipitation, 69, Water: ammonia-free, 176: conductivity,
70. preparation by mixed resin method,
Transmission, 600, 60l. 178: distilled, 177: types of, and
Tropaeolin Q, 55. pH, 51, 53: weight of 1 ml. at various
Tungsten, D. of : as barium tungstate (g), temperatures, table of, 164: weight
491,492: as trioxide (g) via benzidine (brass weights in air) to give 1 litre
complex, 491; via tannin and anti- at 20 C., 194.
pyrine complexes, 491, 492: as Water in inorganic compounds, D. with
tungstyl oxinate (g), 491, 492: by Karl Fischer reagent, 767.
lead amalgam and potassium per- Water of hydration, D. of (g), 398.
manganate (v), 321 : in steel, 574. Weighing: bottles, 158: bottles, micro,
Turbidimeter, 635. 821, 822: direct, 155: effect of
Turbidimetry, 598, 634. buoyancy of air upon, 162: errors in,
Turbidity method, 76: and end point, 77. 161: of chemical samples, 158:
Tyndall effect, 105. " piggy," 822 : reduction of, to vacuo,
Type metal, D. of antimony and tin in (v), 162, 164.
353. Weighing, methods of: Borda, 160:
direct, 155: Gauss, 160: by point of
Units of area, 873: of length, 873: of rest and sensitivity, 155: by short
mass, 874: of volume, 191, 873. swings, 158: by swings, 157.
Universal indicators, 56. Wiping, electrification due to, 161: of
Uranium, D. of : as uranous uranate U 30S micro-apparatus, 816.
via ammonium diuranate (g), 470; Witt plate, 212.
via cupferron complex (g), 470, 471 :
by Jones reductor and potassium Xylene cyanol FF, 301.
permanganate or eerie sulphate (v),
318: by oxine (g), 470, 471; (v), Zero point of balance, determination of,
470. 155, 156.
Uranyl' magnesium acetate, 484: zinc Zimmermann-Rheinhardt process, 269,
acetate, 483. 282: solution, 269.
Urea, D. of: by nitrometer (gv), 812. Zinc amalgam, liquid: preparation of,
320: use of, 320, 321.
Vanadium, D. of: as mercurous vanadate Zinc, D. of : as anthranilate (g), 464, 467 :
(g), 469: as phosphotungstovanadic as hydroxyquinaldinate (g), 465, 467 :
acid (c), 650, 651: as silver vanadate as metal (e), 463, 524: as ZnNH.PO,
(g), 469, 470: by hydrogen peroxide or as pyrophosphate (g), 463, 465: as
(c), 650, 651: by Jones reductor and pyridine thiocyanate (g), 464, 466:
potassium permanganate (v), 319: as quinaldinate (g), 464, 466: as
.. ,~y potassium iodate (v), 367: by sulphide (g), 464, 465: by oxine (g),
sulphur diox~e and potassium per- 375; (v), 374: by standard potas-
918 Index
f _-
sium ferro cyanide solution (v), 379: ZirCOnium. D. 01: as dioxide (g) via basic
in an aluminium alloy, 582: in nickel s)lenite, 476, 477; via para.hydroxy-
silver, 563: in a silver coinage alloy, phenylarsonate (g), 476; via mande-
566. lll.te, 476, 477; via n-propylarsonate,
Zinc dust, evaluation of (gv), 812. 476: as normal selenite (g), 476;
Zinc spirals, amalgamated: preparation (v). 390: as pyrophosphate (g), 475,
of, 225: use of, 225. 477: in steel, 577.
r
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